Use of Metal Complexes Having Bispyridylpyrimidine or Bispyridyltriazine Ligands as Catalysts for Reactions With Peroxy Compounds for Bleaching Coloured Stains on Hard Surfaces

ABSTRACT

The present invention relates to the use of certain manganese complexes having bispyridylpyrimidine or bispyridyltriazine ligands or mixtures of such ligands as catalysts for reactions with peroxy compounds for bleaching coloured stains on hard surfaces, especially dishes in automatic dishwashers. The invention relates also to cleaning formulations for hard surfaces comprising such catalysts.

The present invention relates to the use of certain manganese complexeshaving bispyridylpyrimidine or bispyridyltriazine ligands or mixtures ofsuch ligands as catalysts for reactions with peroxy compounds forbleaching coloured stains on hard surfaces, especially dishes inautomatic dishwashers. The invention also relates to cleaningformulations for hard surfaces comprising such catalysts.

Inorganic peroxy compounds, especially hydrogen peroxide and solidperoxy compounds that dissolve in water with the release of hydrogenperoxide, such as sodium perborate and sodium carbonate perhydrate, havelong been used as oxidising agents for disinfection and bleachingpurposes. The oxidising action of such substances in dilute solutions ishighly dependent upon temperature. For example, using H₂O₂ or perboratein alkaline bleaching liquors it is only at temperatures above about 80°C. that sufficiently rapid bleaching of soiled hard surfaces isachieved. At lower temperatures, the oxidising action of the inorganicperoxy compounds can be improved by the addition of so-called bleachactivators, for which numerous proposals have been disclosed in theliterature. They are especially compounds from the substance classes ofthe N- and O-acyl compounds, for example polyacylated alkylenediamines,especially tetraacetylethylenediamine, acylated glycolurils, especiallytetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles,hydrotriazines, urazoles, diketopiperazines, sulfurylamides andcyanurates, and in addition carboxylic acid anhydrides, especiallyphthalic anhydride, carboxylic acid esters, especially sodiumnonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate, andacylated sugar derivatives, such as pentaacetylglucose. By the additionof such substances, the bleaching action of aqueous peroxide liquors canbe increased to such an extent that even at temperatures of around 60°C. their action is substantially the same as that of the peroxide liquoralone at 95° C.

Those temperatures are still too high for cleaning hard surfaces, forexample table- and kitchen-ware, by hand and are normally not alwaysachieved even in machine dishwashing methods. In the search forenergy-saving methods of cleaning table- and kitchen-ware by machine, inrecent years temperatures of less than 60° C., especially less than 50°C., have been gaining importance.

At such low temperatures the action of the previously known activatorcompounds usually declines noticeably, especially in the case of stainsthat are difficult to bleach, such as tea residues on porcelain orglass. There has therefore been no lack of efforts to develop activatorsthat are more effective in that temperature range, but without therehaving been any convincing success to date.

A starting point might be provided by the use of transition metal saltsand complexes as so-called bleach catalysts. WO 97/07191 alreadydiscloses cleaning formulations for table- and kitchen-ware thatcomprise transition metal complexes of the salen type as activators forperoxy compounds, but those compounds too are still unable to meet allrequirements.

The aim of the present invention was accordingly to provide improvedmetal complex catalysts for oxidation processes that meet the aboverequirements and, especially, enhance the action of peroxide compoundsin automatic dishwashing machines without causing any appreciabledamage.

The addition of complexes of the present invention in catalytic amountsto a dishwashing formulation that comprises a peroxy compound andoptionally TAED (N,N,N′,N′-tetraacetylethylenediamine) or other bleachactivators results in the substantial removal of tea stains fromporcelain in a dishwasher. This is the case even when hard water isused, it being known that tea deposits are more difficult to remove inhard water than in soft water.

The invention accordingly relates to the use of at least one metalcomplex of formula (1)[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1),whereinMe is manganese, titanium, iron, cobalt, nickel or copper,X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8,p is an integer having a value of from 0 to 32,z is the charge of the metal complex,Y is a counter-ion,q=z/(charge of Y), andL is a ligand of formula (2)

whereinQ is N or CR₁₀,R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are each independently of theothers hydrogen; unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl; cyano; halogen; nitro; —COOR₁₁ or—SO₃R₁₁ wherein

-   -   R₁₁ is in each case hydrogen, a cation or unsubstituted or        substituted C₁-C₁₈alkyl or unsubstituted or substituted aryl;        —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein    -   R₁₂ is in each case hydrogen or unsubstituted or substituted        C₁-C₁₈alkyl or unsubstituted or substituted aryl;        —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;        —(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄; —N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂;        —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or        —N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein    -   R₁₂ is as defined above and    -   R₁₃, R₁₄ and R₁₅ are each independently of the other(s) hydrogen        or unsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or        substituted aryl, or    -   R₁₃ and R₁₄, together with the nitrogen atom linking them, form        an unsubstituted or substituted 5-, 6- or 7-membered ring which        may contain further hetero atoms,        as catalyst(s) for bleach reactions in cleaning formulations for        hard surfaces.

Preferably the compounds of formula (1) are used as catalysts for bleachreactions in dishwashing formulations. Such dishwashing formulations arepreferably used in automatic dishwashing machines.

Suitable substituents for the alkyl groups, aryl groups, alkylene groupsor 5-, 6- or 7-membered rings are especially C₁-C₄alkyl; C₁-C₄alkoxy;hydroxy; sulfo; sulfato; halogen; cyano; nitro; carboxy; amino; N-mono-or N,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; N-phenylamino; N-naphthylamino; phenyl; phenoxy ornaphthyloxy.

The C₁-C₁₈alkyl radicals mentioned for the compounds of formula (2) are,for example, straight-chain or branched alkyl radicals, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl orstraight-chain or branched pentyl, hexyl, heptyl or octyl. Preference isgiven to C₁-C₁₂alkyl radicals, especially C₁-C₈alkyl radicals andpreferably C₁-C₄alkyl radicals. The mentioned alkyl radicals may beunsubstituted or substituted e.g. by hydroxy, C₁-C₄alkoxy, sulfo or bysulfato, especially by hydroxy. The corresponding unsubstituted alkylradicals are preferred. Very special preference is given to methyl andethyl, especially methyl.

Examples of aryl radicals that come into consideration for the compoundsof formula (2) are phenyl or naphthyl each unsubstituted or substitutedby C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro, carboxy, sulfo,hydroxy, amino, N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted orsubstituted by hydroxy in the alkyl moiety, N-phenylamino,N-naphthylamino, wherein the amino groups may be quaternised, phenyl,phenoxy or by naphthyloxy. Preferred substituents are C₁-C₄alkyl,C₁-C₄alkoxy, phenyl and hydroxy. Special preference is given to thecorresponding phenyl radicals.

The C₁-C₆alkylene groups mentioned for the compounds of formula (2) are,for example, straight-chain or branched alkylene radicals, such asmethylene, ethylene, n-propylene or n-butylene. C₁-C₄alkylene groups arepreferred. The alkylene radicals mentioned may be unsubstituted orsubstituted, for example by hydroxy or C₁-C₄alkoxy.

In the compounds of formulae (1) and (2), halogen is preferablychlorine, bromine or fluorine, with special preference being given tochlorine.

Examples of cations that come into consideration for compounds offormulae (1) and (2) include alkali metal cations, such as lithium,potassium and especially sodium, alkaline earth metal cations, such asmagnesium and calcium, and ammonium cations. The alkali metal cations,especially sodium, are preferred.

Suitable metal ions for Me for the compounds of formula (1) are, forexample, manganese in oxidation states II-V, titanium in oxidationstates III and IV, iron in oxidation states I to IV, cobalt in oxidationstates I to III, nickel in oxidation states I to III and copper inoxidation states I to III, with special preference being given tomanganese, especially manganese in oxidation states II to IV, preferablyin oxidation state II. Also of interest are titanium IV, iron II-IV,cobalt II-III, nickel II-III and copper II-III, especially iron II-IV.

For the radical X for the compounds of formula (1) there come intoconsideration, for example, CH₃CN; H₂O; F⁻; Cl⁻; Br⁻; HOO⁻; O₂ ²⁻; O²⁻;R₁₆COO⁻; R₁₆O⁻; LMeO⁻ and LMeOO⁻, wherein R₁₆ is hydrogen,—SO₃C₁-C₄alkyl or unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl, and C₁-C₁₈alkyl, aryl, L and Me havethe definitions and preferred meanings given hereinabove and hereinbelow. Especially preferably, R₁₆ is hydrogen; C₁-C₄alkyl; sulfophenylor phenyl, especially hydrogen.

As counter-ion Y for the compounds of formula (1) there come intoconsideration, for example, R₁₇COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₁₇SO₃ ⁻;R₁₇SO₄ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻, Br⁻ and I⁻, wherein R₁₇ is hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl. R₁₇ as C₁-C₁₈alkyl or aryl has the definitions and preferredmeanings given hereinabove and herein below. Especially preferably, R₁₇is hydrogen; C₁-C₄alkyl; phenyl or sulfophenyl, especially hydrogen or4-sulfophenyl. The charge of the counter-ion Y is accordingly preferably1- or 2-, especially 1-.

Y can also be a customary organic counter-ion, for example citrate,oxalate or tartrate. For the compounds of formula (1), n is preferablyan integer having a value of from 1 to 4, preferably 1 or 2 andespecially 1.

For the compounds of formula (1), m is preferably an integer having avalue of 1 or 2, especially 1.

For the compounds of formula (1), p is preferably an integer having avalue of from 0 to 4, especially 2.

For the compounds of formula (1), z is preferably an integer having avalue of from 8− to 8+, especially from 4− to 4+ and especiallypreferably from 0 to 4+. z is more especially the number 0.

For the compounds of formula (1), q is preferably an integer from 0 to8, especially from 0 to 4, and is especially preferably the number 0.

R₁₁ in compounds of formula (2) is preferably hydrogen, a cation,C₁-C₁₂alkyl, unsubstituted phenyl or phenyl substituted as indicatedabove. Especially preferably, R₁₁ is hydrogen, an alkali metal cation,alkaline earth metal cation or ammonium cation, C₁-C₄alkyl or phenyl,especially hydrogen or an alkali metal cation, alkaline earth metalcation or ammonium cation.

R₁₂ in compounds of formula (2) is preferably hydrogen, C₁-C₁₂alkyl,unsubstituted phenyl or phenyl substituted as indicated above.Especially preferably, R₁₂ is hydrogen, C₁-C₄alkyl or phenyl, moreespecially hydrogen or C₁-C₄alkyl, preferably hydrogen. Examples of theradical of formula —OR₁₂ that may be mentioned are hydroxy andC₁-C₄alkoxy, such as methoxy and especially ethoxy.

When R₁₃ and R₁₄ in compounds of formula (2), together with the nitrogenatom linking them, form a 5-, 6- or 7-membered ring, that ring ispreferably an unsubstituted or C₁-C₄alkyl-substituted pyrrolidine,piperidine, piperazine, morpholine or azepane ring, wherein the aminogroups may be quaternised, in which case preferably the nitrogen atomsthat are not bonded directly to one of the three rings A, B or C arequaternised.

The piperazine ring may, for example, be substituted by one or twounsubstituted C₁-C₄alkyl and/or substituted C₁-C₄alkyl at the nitrogenatom not bonded to the pyridine ring. In addition, R₁₃, R₁₄ and R₁₅ arepreferably hydrogen, unsubstituted or hydroxy-substituted C₁-C₁₂alkyl,unsubstituted phenyl or phenyl substituted as indicated above. Specialpreference is given to hydrogen, unsubstituted or hydroxy-substitutedC₁-C₄alkyl or unsubstituted or hydroxy-substituted phenyl, especiallyhydrogen or unsubstituted or hydroxy-substituted C₁-C₄alkyl, preferablyhydrogen.

Preference is given to ligands L of formula (2) wherein R₅ is nothydrogen.

R₅ in L of formula (2) is preferably C₁-C₁₂alkyl; phenyl unsubstitutedor substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, cyano, nitro,carboxy, sulfo, hydroxy, amino, N-mono- or N,N-di-C₁-C₄alkylaminounsubstituted or substituted by hydroxy in the alkyl moiety,N-phenyl-amino, N-naphthylamino, phenyl, phenoxy or by naphthyloxy;cyano; halogen; nitro; —COOR₁₁ or —SO₃R₁₁ wherein R₁₁ is in each casehydrogen, a cation, C₁-C₁₂alkyl, unsubstituted phenyl or phenylsubstituted as indicated above; —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein R₁₂ isin each case hydrogen, C₁-C₁₂alkyl, unsubstituted phenyl or phenylsubstituted as indicated above; —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄;—N^(⊕)R₁₃R₁₄R₁₅; —(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;—N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;—N(R₁₂)—N—R₁₃R₁₄ or —N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein R₁₂ may have one ofthe meanings given above and R₁₃, R₁₄ and R₁₅ are each independently ofthe other(s) hydrogen, unsubstituted or hydroxy-substituted C₁-C₁₂alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ringunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl, wherein the nitrogen atom may bequaternised.

R₅ in L of formula (2) is especially preferably phenyl unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, phenyl or by hydroxy;cyano; nitro; —COOR₁₁ or —SO₃R₁₁ wherein R₁₁ is in each case hydrogen, acation, C₁-C₄alkyl or phenyl; —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein R₁₂ is ineach case hydrogen, C₁-C₄alkyl or phenyl; —N(CH₃)—NH₂ or —NH—NH₂; amino;N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety; or an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring.

R₅ in L of formula (2) is very especially preferably C₁-C₄alkoxy;hydroxy; phenyl unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,phenyl or by hydroxy; hydrazine; amino; N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; or an unsubstituted or C₁-C₄alkyl-substituted pyrrolidine,piperidine, piperazine, morpholine or azepane ring.

As radicals R₅ in L of formula (2) there are especially importantC₁-C₄alkoxy; hydroxy; hydrazine; amino; N-mono- orN,N-di-C₁-C₄alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; and an unsubstituted or C₁-C₄alkyl-substitutedpyrrolidine, piperidine, piperazine, morpholine or azepane ring.

As radicals R₅ in L of formula (2) there are very especially importantC₁-C₄alkoxy; hydroxy; N-mono- or N,N-di-C₁-C₄alkylamino substituted byhydroxy in the alkyl moiety; and an unsubstituted orC₁-C₄alkyl-substituted pyrrolidine, piperidine, piperazine, morpholineor azepane ring. Of those, hydroxy is of special interest.

The preferred meanings given above for R₅ apply also to R₁, R₂, R₃, R₄,R₆, R₇, R₈, R₉ and R₁₀ in L of formula (2), but those radicals mayadditionally be hydrogen.

According to one embodiment of the present invention, R₁, R₂, R₃, R₄,R₆, R₇, R₈, R₉ and R₁₀ in L of formula (2) are hydrogen and R₅ in L offormula (2) is a radical other than hydrogen having the definition andpreferred meanings indicated above.

According to a further embodiment of the present invention, R₁, R₂, R₄,R₆, R₈, R₉ and R₁₀ in L of formula (2) are hydrogen and R₃, R₅ and R₇ inL of formula (2) are radicals other than hydrogen, for each of which thedefinition and preferred meanings indicated above for R₅ apply.

Preferred as ligands L are those of formula (3a) and/or (3b)

wherein R′₃ and R′₇ have the definitions and preferred meaningsindicated above for R₃ and R₇, and R′₅ has the definition and preferredmeanings indicated above for R₅.

A preferred embodiment of the present invention relates to the use of atleast one Mn(II)-complex of formula (3c) and/or (3d)

wherein

-   -   R′₅ is hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino unsubstituted        or substituted by hydroxy in the alkyl moiety; or —NR₁₃R₁₄;        —(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;        —N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein        -   R₁₂ is hydrogen; C₁-C₄alkyl or unsubstituted phenyl or            phenyl substituted by (substituted in the alkyl moiety by            hydroxy) N-mono- or N,N-di-C₁-C₂alkylamino-, N-phenylamino-,            N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and        -   R₁₃ and R₁₄ are each independently of the other hydrogen,            unsubstituted or hydroxy-substituted C₁-C₄alkyl,            unsubstituted phenyl or phenyl substituted as indicated            above, or        -   R₁₃ and R₁₄, together with the nitrogen atom linking them,            form a pyrrolidine, piperidine, piperazine, morpholine or            azepane ring that is unsubstituted or substituted by at            least one unsubstituted C₁-C₄alkyl and/or substituted            C₁-C₄alkyl, especially a pyrrolidine, piperidine,            piperazine, morpholine or azepane ring, and    -   R′₃ and R′₇ are each independently of the other hydrogen;        halogen; hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino substituted        by hydroxy in the alkyl moiety; or —NR₁₃R₁₄;        —(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;        —N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein        -   R₁₂ is hydrogen; C₁-C₄alkyl or unsubstituted phenyl or            phenyl substituted by (substituted in the alkyl moiety by            hydroxy) N-mono- or N,N-di-C₁-C₂alkylamino-, N-phenylamino-,            N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and        -   R₁₃ and R₁₄ are each independently of the other hydrogen;            unsubstituted or hydroxy-substituted C₁-C₄alkyl,            unsubstituted phenyl or phenyl substituted as indicated            above, or        -   R₁₃ and R₁₄, together with the nitrogen atom linking them,            form a pyrrolidine, piperidine, piperazine, morpholine or            azepane ring that is unsubstituted or substituted by at            least one unsubstituted C₁-C₄alkyl and/or substituted            C₁-C₄alkyl, especially a pyrrolidine, piperidine,            piperazine, morpholine or azepane ring,            X is F⁻; Cl⁻; Br⁻; HOO⁻; ⁻CH₃COO⁻; HCOO⁻ or HO⁻, and            Y is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻;            NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻.

A more preferred embodiment of the present invention relates to the useof at least one Mn(II)-complex of formula (3c) and/or (3d)

wherein

-   R′₅ is hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino unsubstituted or    substituted by hydroxy in the alkyl moiety; or —NH₂    -   R₁₃ and R₁₄ are each independently of the other hydrogen,        unsubstituted or-   R₁₃ and R₁₇ are each independently of the other hydrogen; Cl;    hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino substituted by hydroxy in    the alkyl moiety;-   X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and-   Y is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻;    F⁻; Cl⁻; Br⁻ or I⁻.

An embodiment of the invention to which preference is likewise given isthe use of at least one metal complex compound of formula (1′)[L′_(n)Me_(m)X_(p)]^(z)Y_(q)  (1′),whereinMe is manganese, titanium, iron, cobalt, nickel or copper,X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8,p is an integer having a value of from 0 to 32,z is the charge of the metal complex,Y is a counter-ion,q=z/(charge of Y), andL′ is a ligand of formula (2′)

whereinQ is N or CR₁₀,R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are each independently of theothers hydrogen; unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl; cyano; halogen; nitro; —COOR₁, or—SO₃R₁₁ wherein

-   -   R₁₁ is in each case hydrogen, a cation or unsubstituted or        substituted C₁-C₁₈alkyl or unsubstituted or substituted aryl;        —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein    -   R₁₂ is in each case hydrogen or unsubstituted or substituted        C₁-C₁₈alkyl or unsubstituted or substituted aryl;        —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;        —(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄; —N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂;        —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or        —N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein    -   R₁₂ is as defined above and    -   R₁₃, R₁₄ and R₁₅ are each independently of the other(s) hydrogen        or unsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or        substituted aryl, or    -   R₁₃ and R₁₄, together with the nitrogen atom linking them, form        an unsubstituted or substituted 5-, 6- or 7-membered ring which        may contain further hetero atoms,        with the proviso that        at least one of the substituents R₁ to R₁₀ contains a        quaternised nitrogen atom that is not bonded directly to one of        the three rings A, B and/or C,        as catalyst(s) for bleach reactions in cleaning formulations for        hard surfaces.

Preferably the compounds of formula (1′) are used as catalysts forbleach reactions in dishwashing formulations. Such dishwashingformulations are preferably used in automatic dishwashing machines.

The preferences for all substituents of formula (1′) are the same as forthose of the compound of formula (1), which are disclosed in page 2-page8.

As examples of the radical R₅ in L′ of formula (2′) mention may be madeespecially —OH;

Of those, hydroxy is of special interest.

The preferred meanings given above for R₅ in L′ of formula (2′) applyalso to R₁, R₂, R₃, R₄, R₅, R₇, R₈, R₉ and R₁₀ in L′ of formula (2′),but those radicals may additionally be hydrogen.

In accordance with one embodiment of the present invention, R₁, R₂, R₃,R₄, R₆, R₇, R₈, R₉ and R₁₀ in L′ of formula (2′) are hydrogen and R₅ inL′ of formula (2′) is a radical other than hydrogen having thedefinition and preferred meanings indicated above.

A preferred embodiment of the present invention relates to the use of atleast one Mn(II)-complex of formula (3′c) and/or (3′d)

whereinR₁₅ is

R′₃ and R′₇ are independently of each other are H; Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, R′₅ and R′₇is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, andY is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻;Cl⁻; Br⁻ or I⁻.

A more preferred embodiment of the present invention relates to the useof at least one Mn(II)-complex of formula (3′c) and/or (3′d)

whereinR′₅ is

R′₃ is H; Cl; —OH; —NH₂;

R′₇ is Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, and R′₇ is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, andY is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻;Cl⁻; Br⁻ or I⁻.

Preferred as L′ are compounds of formulae (2′), (3′c) and (3′d) in which1 quarternised nitrogen atom is present.

Also preferred as L′ are compounds of formulae (2′), (3′c) and (3′d) inwhich 2 or 3 quaternised nitrogen atoms are present.

Especially preferred as L′ are compounds of formulae (2′), (3′c) and(3′d) in which none of the quaternised nitrogen atoms is bonded directlyto one of three rings A, B and/or C.

The metal complex compounds of formulae (1) and (1′) can be obtainedanalogously to known processes. They are obtained in a manner known perse by reacting at least one ligand L and/or L′ in the desired molarratio with a metal compound, especially a metal salt, such as thechloride, to form the corresponding metal complex. The reaction iscarried out, for example, in a solvent, such as water or a loweralcohol, such as ethanol, at a temperature of, for example, from 10 to60° C., especially at room temperature.

Ligands L and L′ that are substituted by hydroxy can also be depicted inone or more tautomeric forms in accordance with the following scheme:

Compounds of the bispyridyl-pyrimidine type can also be prepared in amanner known per se [F. H. Case et al., J. Org. Chem. 1967, 32(5),1591-1596]). For that purpose, for example, one partpyridine-2-carboxylate and one part ethyl acetate can be reacted withsodium hydride, and the intermediate obtained after aqueous working-up,a β-keto ester, reacted with 2-amidinopyridine, yielding thecorresponding pyrimidine derivative which can be converted into thechlorine compounds by reaction with a chlorinating agent, such as, forexample, PCl₅/POCl₃. Reaction of those compounds with amines, as desiredin the presence of an excess of redox-active salts of transition metals,such as manganese, iron or ruthenium, in order to acceleratesubstitution, yields amine-substituted bispyridyl-pyrimidines.Preparation procedures using the latter two metal ions are described,for example, in J. Chem. Soc., Dalton Trans. 1990, 1405-1409 (E. C.Constable et al.) and New. J. Chem. 1992, 16, 855-867.

It has now been found that, in order to accelerate replacement of halideby amine on the bispyridyl-pyrimidine structure, it is also possible touse catalytic amounts of non-transition metal salts, such as, forexample, zinc(II) salts, which substantially simplifies the reactionprocedure and working-up.

Compounds of the bispyridyl-triazine type can be prepared analogously toknown processes (e.g. Patent Applications EP 555 180 and EP 556 156 orF. H. Case et al., J. Am. Chem. Soc. 1959, 81, 905-906), by reacting twoparts 2-cyanopyridine with urea or guanidine and a base.

The invention relates also to cleaning formulations for hard surfaces,especially cleaning formulations for table- and kitchen-ware and, amongsuch formulations, preferably those for use in cleaning processescarried out by machine, which formulations comprise one of theabove-described compounds of formula (1a) or (1′a) as bleach catalyst,and to a method of cleaning hard surfaces, especially table- andkitchen-ware, using such a bleach catalyst.

The present invention also relates to hard surface cleaning compositions(C1), preferably dishwashing compositions, comprising at least onecompound of formula (1)[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1),whereinMe is manganese, titanium, iron, cobalt, nickel or copper,X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8,p is an integer having a value of from 0 to 32,z is the charge of the metal complex,Y is a counter-ion,q=z/(charge of Y), andL is a ligand of formula (2)

whereinQ is N or CR₁₀,R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are each independently of theothers hydrogen; unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl; cyano; halogen; nitro; —COOR₁₁ or—SO₃R₁₁ wherein

-   -   R₁₁ is in each case hydrogen, a cation or unsubstituted or        substituted C₁-C₁₈alkyl or unsubstituted or substituted aryl;        —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein    -   R₁₂ is in each case hydrogen or unsubstituted or substituted        C₁-C₁₈alkyl or unsubstituted or substituted aryl;        —NR₁₃R₁₄; —(C₁-C₁₈alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;        —(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄; —N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂;        —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or        —N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein    -   R₁₂ is as defined above and    -   R₁₃, R₁₄ and R₁₅ are each independently of the other(s) hydrogen        or unsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or        substituted aryl, or    -   R₁₃ and R₁₄, together with the nitrogen atom linking them, form        an unsubstituted or substituted 5-, 6- or 7-membered ring which        may contain further hetero atoms.

The above mentioned surface cleaning composition (C1) composition ispreferably a dishwashing composition, more preferably an automaticdishwasher composition.

The preferences for all substituents of formula (1) are the same asdisclosed on page 2-page 8.

A preferred embodiment relates to hard surface cleaning compositions(C2), preferably dishwashing compositions, comprising at least oneMn(II)-complex of formula (3c) and/or (3d)

wherein

-   -   R′₅ is hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino unsubstituted        or substituted by hydroxy in the alkyl moiety; or —NR₁₃R₁₄;        —(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;        —N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein        -   R₁₂ is hydrogen; C₁-C₄alkyl or unsubstituted phenyl or            phenyl substituted by (substituted in the alkyl moiety by            hydroxy) N-mono- or N,N-di-C₁-C₂alkylamino-, N-phenylamino-,            N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and        -   R₁₃ and R₁₄ are each independently of the other hydrogen,            unsubstituted or hydroxy-substituted C₁-C₄alkyl,            unsubstituted phenyl or phenyl substituted as indicated            above, or        -   R₁₃ and R₁₄, together with the nitrogen atom linking them,            form a pyrrolidine, piperidine, piperazine, morpholine or            azepane ring that is unsubstituted or substituted by at            least one unsubstituted C₁-C₄alkyl and/or substituted            C₁-C₄alkyl, especially a pyrrolidine, piperidine,            piperazine, morpholine or azepane ring, and    -   R′₃ and R′₇ are each independently of the other hydrogen;        halogen; hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino substituted        by hydroxy in the alkyl moiety; or —NR₁₃R₁₄;        —(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;        —N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein        -   R₁₂ is hydrogen; C₁-C₄alkyl or unsubstituted phenyl or            phenyl substituted by (substituted in the alkyl moiety by            hydroxy) N-mono- or N,N-di-C₁-C₂alkylamino-, N-phenylamino-,            N-naphthylamino-, phenyl-, phenoxy- or naphthyloxy, and        -   R₁₃ and R₁₄ are each independently of the other hydrogen;            unsubstituted or hydroxy-substituted C₁-C₄alkyl,            unsubstituted phenyl or phenyl substituted as indicated            above, or        -   R₁₃ and R₁₄, together with the nitrogen atom linking them,            form a pyrrolidine, piperidine, piperazine, morpholine or            azepane ring that is unsubstituted or substituted by at            least one unsubstituted C₁-C₄alkyl and/or substituted            C₁-C₄alkyl, especially a pyrrolidine, piperidine,            piperazine, morpholine or azepane ring,            X is F⁻; Cl⁻; Br⁻; HOO⁻; ⁻CH₃COO⁻; HCOO⁻ or HO⁻, and            Y is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻;            NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻.

The above mentioned surface cleaning composition (C2) composition ispreferably a dishwashing composition, more preferably an automaticdishwasher composition.

A more preferred embodiment relates to hard surface cleaningcompositions (C3), preferably dishwashing compositions, comprising atleast one Mn(II)-complex of formula (3c) and/or (3d)

wherein

-   R′₅ is hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino unsubstituted or    substituted by hydroxy in the alkyl moiety; or —NH₂-   R′₃ and R′₇ are each independently of the other hydrogen; Cl;    hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino substituted by hydroxy in    the alkyl moiety;-   X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and-   Y is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻;    F⁻; Cl⁻; Br⁻ or I⁻.

The above mentioned surface cleaning composition (C3) composition ispreferably a dishwashing composition, more preferably an automaticdishwasher composition.

The present invention relates to hardsurface cleaning compositions (C4),preferably dishwashing compositions, comprising at least one metalcomplex compounds of formula (1′)[L′_(n)Me_(m)X_(p)]^(z)Y_(q)  (1′),whereinMe is manganese, titanium, iron, cobalt, nickel or copper,X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8,p is an integer having a value of from 0 to 32,z is the charge of the metal complex,Y is a counter-ion,q=z/(charge of Y), andL′ is a ligand of formula (2′)

whereinQ is N or CR₁₀,R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are each independently of theothers hydrogen; unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl; cyano; halogen; nitro; —COOR₁₁ or—SO₃R₁₁ wherein

-   -   R₁₁ is in each case hydrogen, a cation or unsubstituted or        substituted C₁-C₁₈alkyl or unsubstituted or substituted aryl;        —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein    -   R₁₂ is in each case hydrogen or unsubstituted or substituted        C₁-C₁₈alkyl or substituted or unsubstituted aryl;        —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;        —(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄; —N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂;        —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;        —N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or        —N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein    -   R₁₂ is as defined above and    -   R₁₃, R₁₄ and R₁₅ are each independently of the other(s) hydrogen        or unsubstituted or substituted C₁-C₁₈alkyl or substituted or        unsubstituted aryl, or    -   R₁₃ and R₁₄, together with the nitrogen atom linking them, form        an unsubstituted or substituted 5-, 6- or 7-membered ring which        may contain further hetero atoms, with the proviso that,        at least one of the substituents R₁ to R₁₀ contains a        quaternised nitrogen atom that is not bonded directly to one of        the three rings A, B and/or C.

The above mentioned surface cleaning composition (C4) composition ispreferably a dishwashing composition, more preferably an automaticdishwasher composition.

The preferences for all substituents of formula (1′) are the same asdisclosed on page 2-page 8.

A preferred embodiment relates to hard surface cleaning compositions(C5), preferably dishwashing compositions, more preferably automaticdishwashing compositions, comprising at least one Mn(II)-complex offormula (3′c) and/or (3′d)

whereinR′₅ is

R′₃ and R′₇ are independently of each other are H; Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, R′₅ and R′₇is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, andY is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻;Cl⁻; Br⁻ or I⁻.

The above mentioned surface cleaning composition (C5) composition ispreferably a dishwashing composition, more preferably an automaticdishwasher composition.

A more preferred embodiment relates to hard surface cleaningcompositions (C6), preferably dishwashing compositions, comprising atleast one Mn(II)-complex of formula (3′c) and/or (3′d)

whereinR′₅ is

R′₃ is H; Cl; —OH; —NH₂;

R′₇ is Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, and R′₇ is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, andY is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻;Cl⁻; Br⁻ or I⁻.

The above mentioned surface cleaning composition (C6) composition ispreferably a dishwashing composition, more preferably an automaticdishwasher composition.

Preferred Mn(II)-complexes in the hard surface cleaning composition(C4), (C5) and (C6) have just 1 quaternised nitrogen atom.

Also preferred Mn(II)-complexes in the hard surface cleaning composition(C4), (C5) and (C6) have 2 or 3 quaternised nitrogen atoms.

Especially preferred Mn(II)-complexes in the hard surface cleaningcomposition (C4), (C5) and (C6) are those in which none of thequaternised nitrogen atoms is bonded directly to one of the rings A, Bor C.

The use according to the invention lies essentially in providing, in thepresence of a hard surface soiled with coloured stains, conditions underwhich a peroxide-containing oxidising agent and the bleach catalystaccording to formulae (1) and/or (1′) are able to react with one anotherwith the aim of obtaining resulting products having a more stronglyoxidising action. This can be brought about by separately adding theperoxy compound and the bleach catalyst to a formulation, which mayoptionally contain cleaning formulation. The method according to theinvention is, however, advantageously carried out using a cleaningformulation for hard surfaces according to the invention that comprisesthe bleach catalyst and a peroxy-containing oxidising agent. The peroxycompound can also be added to the formulation separately, as such or inthe form of a preferably aqueous formulation or suspension, when aperoxide-free cleaning formulation is used.

Depending upon the intended use, the conditions can be widely varied.For example, in addition to purely aqueous solutions, mixtures of waterand suitable organic solvents also come into consideration as reactionmedium. The amounts of peroxy compounds used are generally so selectedthat from 10 ppm (wherein ppm denoted parts per million by weight) to10% active oxygen, preferably from 50 ppm to 5000 ppm active oxygen, arepresent in the solutions. The amount of bleach catalyst used alsodepends upon the intended use.

Depending upon the desired degree of activation, from 0.00001 mol to0.025 mol, preferably from 0.0001 mol to 0.1 mol, of catalyst is usedper mole of peroxy compound, but in special cases amounts above or belowthose limits may also be used.

The hard surface cleaning compositions, preferably dishwashingcompositions herein can have any desired physical form; when in granularform, it is typical to limit water content, for example to less thanabout 10%, preferably less than about 7% free water, for best storagestability.

Unless otherwise indicated, the hard surface cleaning compositions ofthe invention may for example, be formulated as granular or power-formall-purpose; liquid, gel or paste-form; hand dishwashing agents or lightduty dishwashing agents, especially those of the high-foaming type;machine dishwashing agents, including the various tabletted, granular,liquid and rinse-aid types for household and institutional use; liquidcleaning and disinfecting agents, including antibacterial hand-washtypes, bathroom cleaners; as well as cleaning auxiliaries such as bleachadditives and “stain-stick” or pre-treat types.

The invention relates also to a cleaning formulation for hard surface,preferably to a dishwashing formulation, more preferably to an automaticdishwashing formulation (especially for table- and kitchen-ware), thatcomprises from 0.001% by weight (wt-%) to 1 wt-%, especially from 0.005wt-% to 0.1 wt-%, bleach catalyst according to formulae (1) and/or (1′)in addition to customary ingredients compatible with the bleachcatalyst. The weight percentages are based on the total weight of thecleaning formulation. The bleach catalyst may, in a manner known inprinciple, be adsorbed on carriers and/or embedded in encapsulatingsubstances.

The cleaning formulations according to the invention, which can be inthe form of powder- or tablet-form solids, or homogeneous solutions orsuspensions, may in principle comprise, in addition to the bleachcatalyst used according to the invention, any known ingredientscustomary in such formulations. The formulations according to theinvention may comprise especially builder substances, surface-activesurfactants, peroxy compounds, water-miscible organic solvents, enzymes,sequestering agents, electrolytes, pH regulators and further adjuvants,such as silver-corrosion inhibitors, foam regulators, additional peroxyactivators and also colourings and perfumes.

A cleaning formulation for hard surfaces according to the invention canalso comprise abrasive constituents, especially from the groupcomprising quartz powders, wood flours, ground plastics, chalks andglass microbeads, and mixtures thereof. Abrasive substances are presentin the cleaning formulations according to the invention preferably inamounts not exceeding 20 wt-%, especially in amounts of from 5 wt-% to15 wt-%.

Amounts of the essential ingredients can vary within wide ranges,however preferred hard surface cleaning compositions, preferablydishwashing detergent compositions, more preferably automaticdishwashing detergent compositions, herein (which typically have a 1%aqueous solution pH of above 8, more preferably from 9.0 to 12, mostpreferably from 9.5 to 10.5) are those wherein there is present:

-   from 5 wt-% to 90 wt-%, preferably from 5 wt-% to 75 wt-%, of at    least one builder;-   from 0.1 wt-% to 40 wt-%, preferably from 0.5 wt-% to 30 wt-%, of at    least one oxygen-based bleaching agent;-   from 0.1 wt-% to 15 wt-%, preferably from 0.2 wt-% to 10 wt-%, of    the surfactant system;-   from 0.0001 wt-% to 1 wt-%, preferably from 0.001 wt-% to 0.05 wt-%,    of at least one metal-containing bleach catalyst as described above;    and-   from 0.1 wt-% to 40 wt-%, preferably from 0.1 wt-% to 20 wt-% of an    alkaline carrier.

All wt-%'s relate to the total weight of the surface cleaningcompositions, preferably dishwashing detergent compositions, and morepreferably automatic dishwashing detergent compositions.

Such fully-formulated embodiments typically further comprise from 0.1wt-% to 15 wt-% of a polymeric dispersant, from 0.01 wt-% to 10 wt-% ofa chelant, and from 0.00001 wt-% to 10 wt-% of a detersive enzyme,though further additional or adjunct ingredients may be present.Preferred hard surface cleaning compositions, preferably dishwashingdetergent compositions, more preferably automatic dishwashing detergentcompositions herein in granular form typically limit water content, forexample to less than 7 wt-% free water, for best storage stability. Allwt-%'s relate to the total weight of the surface cleaning compositions.

Water-soluble builder components that come into consideration in suchlow-alkalinity cleaning formulations include, in principle, any builderscustomarily used in machine dishwashing formulations, for examplepolymeric alkali metal phosphates, which may be in the form of theiralkaline, neutral or acidic sodium or potassium salts. Examples thereofare tetrasodium diphosphate, disodium dihydrogen diphosphate,pentasodium triphosphate, sodium tripolyphosphate, so-called sodiumhexametaphosphate and the corresponding potassium salts as well asmixtures of sodium and potassium salts. They may be present in amountsin the range of up to about 35 wt-%, based on the total formulation.Other possible builder components include the various water-soluble,alkali metal, ammonium or substituted ammonium borates,hydroxysulfonates and polyacetates. Preferred are the alkali metals,especially sodium, salts of such materials. Further possiblewater-soluble builder components are, for example, organic polymers ofnatural or synthetic origin, especially polycarboxylates, which,particularly in hard water areas, act as co-builders. There come intoconsideration, for example, polyacrylic acids and copolymers of maleicanhydride and acrylic acid and also the sodium salts of those polymericacids. Commercially available products are, for example, Sokalan® CP 5and PA 30 from BASF. Polymers of natural origin that can be used asco-builders include, for example, oxidised starch, as known, forexample, from International Patent Application WO 94/05762, andpolyamino acids, such as polyglutamic acid or polyaspartic acid. Furtherpossible builder components are naturally occurring hydroxycarboxylicacids, e.g. mono- and di-hydroxysuccinic acid, α-hydroxypropionic acidand gluconic acid. There also come into consideration as buildercomponents the salts of citric acid, especially sodium citrate. Assodium citrate there come into consideration anhydrous trisodium citrateand especially trisodium citrate dihydrate. Trisodium citrate dihydratecan be used in the form of a fine- or coarse-crystalline powder.Depending upon the pH value ultimately established in the formulationsaccording to the invention, the acids corresponding to the mentionedco-builder salts may also be present. Alternate water-soluble,non-phosphorus organic builders can be used for their sequesteringproperties. Examples of polyacetate and polycarboxylate builders are thesodium, potassium, lithium, ammonium and substituted ammonium salts ofethylenediamine tetraacetic acid; nitrilotriacetic acid, tartratemonosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid,carboxymethyloxysuccinic acid, mellitic acid, and sodium benzenepolycarboxylate salts. Oxygen-based bleaching agents that come intoconsideration include alkali metal perborate, commercially available,e.g., in the form of mono- or tetra-hydrate; urea peroxyhydrate, alkalimetal percarbonate, and sodium peroxide. Hydrogen peroxide sources aredescribed in detail in the herein incorporated Kirk Othmer'sEncyclopedia of Chemical Technology, 4^(th) Ed (1992, John Wiley &Sons), Vol. 4, pp. 271-300 “Bleaching Gents (Survey)”. Particularlypreferred are sodium perborate tetrahydrate, sodium perboratemonohydrate and sodium percarbonate. Percarbonate is especiallypreferred because of environmental issues associated with boron.

Highly preferred percarbonate can be in uncoated or coated form. Theaverage particle size of uncoated percarbonate ranges from about 400 toabout 1200 microns, most preferably from about 400 to about 600 microns.

The use of sodium percarbonate has advantages especially in cleaningformulations for table- and kitchen-ware, since it has a particularlyadvantageous effect on corrosion behaviour in glasses.

In addition, or especially alternatively, it is also possible for knownperoxycarboxylic acids to be present, for example dodecane-diperacid orphthalimidoperoxycarboxylic acids, which may be unsubstituted orsubstituted on the aromatic moiety. Furthermore, the addition of smallamounts of known bleaching agent stabilisers, for example phosphonates,borates or metaborates and metasilicates, and also magnesium salts, suchas magnesium sulfate, may be advantageous.

As surfactant system, at least one surfactant selected from the listincluding anionic, nonionic, cationic, amphoteric, and zwitterionicsurfactants is used. Such surfactants are well known in the detergentarts and are described at length in “Surface Active Agents andDetergents”, Vol. 2 by Schwartz, Perry and Birch, IntersciencePublishers, Inc.; 1959, herein incorporated by reference. Low foamingsurfactants are most suitable for machine dishwashing applications.

Preferred surfactants are one or a mixture of:

Anionic Surfactants

Anionic synthetic detergents can be broadly described as surface activecompounds with one or more negatively charged functional groups. Animportant class of anionic compounds are the water-soluble salts,particularly the alkali metal salts, of organic sulfur reaction productshaving in their molecular structure an alkyl radical containing fromabout 6 to 24 carbon atoms and a radical selected from the groupconsisting of sulfonic and sulfuric acid ester radicals.

Primary Alkyl SulfatesR_(α)OSO₃M,whereinR_(α) is a primary alkyl group of 8 to 18 carbon atoms and M is asolubilizing cation.

The alkyl group R_(α) may have a mixture of chain lengths. It ispreferred that at least two-thirds of the R_(α) alkyl groups have achain length of 8 to 14 carbon atoms. This will be the case if R_(α) iscoconut alkyl, for example. The solubilizing cation may be a range ofcations which are in general monovalent and confer water solubility. Analkali metal, notably sodium, is especially envisaged. Otherpossibilities are ammonium and substituted ammonium ions, such astrialkanolammonium or trialkylammonium.

Alkyl Ether SulfatesR_(α)O(CH₂CH₂O)_(n)SO₃M,whereinR_(α) is a primary alkyl group of 8 to 18 carbon atoms,n has an average value in the range from 1 to 6 andM is a solubilizing cation.

The alkyl group R_(α) may have a mixture of chain lengths. It ispreferred that at least two-thirds of the R_(α) alkyl groups have achain length of 8 to 14 carbon atoms. This will be the case if R_(α) iscoconut alkyl, for example. Preferably n has an average value of 2 to 5.

Fatty Acid Ester SulfonatesR_(β)CH(SO₃M)CO₂R_(χ),whereinR_(β) is an alkyl group of 6 to 16 atoms,R_(χ) is an alkyl group of 1 to 4 carbon atoms andM is a solubilizing cation.

The group R_(β) may have a mixture of chain lengths. Preferably at leasttwo-thirds of these groups have 6 to 12 carbon atoms. This will be thecase when the moiety R_(β)CH(−)CO₂(−) is derived from a coconut source,for instance. It is preferred that R_(χ) is a straight chain alkyl,notably methyl or ethyl.

Alkyl Benzene SulfonatesR_(δ)ArSO₃M,whereinR_(δ) is an alkyl group of 8 to 18 carbon atoms,Ar is a benzene ring (C₆H₄) andM is a solubilizing cation.

The group R_(δ) may be a mixture of chain lengths. Straight chains of 11to 14 carbon atoms are preferred.

Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16carbon atoms, in the alkyl moiety. These surfactants are commerciallyavailable as Hostapur® SAS from Clariant.

Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16carbon atoms. U.S. Pat. No. 3,332,880 contains a description of suitableolefin sulfonates.

Organic phosphate based anionic surfactants include organic phosphateesters such as complex mono- or diester phosphates ofhydroxyl-terminated alkoxide condensates, or salts thereof, included inthe organic phosphate esters are phosphate ester derivatives ofpolyoxyalkylated alkylaryl phosphate esters, of ethoxylated linearalcohols and ethoxylates of phenol. Also included are nonionicalkoxylates having a sodium alkylenecarboxylate moiety linked to aterminal hydroxyl group of the nonionic through an ether bond.Counterions to the salts of all the foregoing may be those of alkalimetal, alkaline earth metal, ammonium, alkanolammonium and alkylammoniumtypes.

Particularly preferred anionic surfactants are the fatty acid estersulfonates with formula:R_(β)CH(SO₃M)CO₂R_(χ),whereinthe moiety R_(β)CH(−)CO₂(−) is derived from a coconut source andR_(χ) is either methyl or ethyl; primary alkyl sulfates with theformula:R_(α)OSO₃M, whereinR_(α) is a primary alkyl group of 10 to 18 carbon atoms andM is a sodium cation; and paraffin sulfonates, preferably with 12 to 16carbon atoms to the alkyl moiety.Nonionic Surfactants

Nonionic surfactants can be broadly defined as surface active compoundswith one or more uncharged hydrophilic substituents. A major class ofnonionic surfactants consists of those compounds produced by thecondensation of alkylene oxide groups with an organic hydrophobicmaterial which may be aliphatic or alkyl aromatic in nature. The lengthof the hydrophilic or polyoxyalkylene radical which is condensed withany particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements. Illustrative, but not limitingexamples, of various suitable nonionic surfactant types are:

Polyoxyalkene condensates of aliphatic carboxylic acids, whether linear-or branched-chain and unsaturated or saturated, especially ethoxylatedand/or propoxylated aliphatic acids containing from about 8 to about 18carbon atoms in the aliphatic chain and incorporating from about 2 toabout 50 ethylene oxide and/or propylene oxide units. Suitablecarboxylic acids include “coconut” fatty acids (derived from coconutoil) which contain an average of about 12 carbon atoms, “tallow” fattyacids (derived from tallow-class fats) which contain an average of about18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauricacid.

Polyoxyalkene condensates of aliphatic alcohols, whether linear- orbranched-chain and unsaturated or saturated, especially ethoxylatedand/or propoxylated aliphatic alcohols containing from about 6 to about24 carbon atoms and incorporating from about 2 to about 50 ethyleneoxide and/or propylene oxide units. Suitable alcohols include “coconut”fatty alcohol, “tallow” fatty alcohol, lauryl alcohol, myristyl alcoholand oleyl alcohol.

Ethoxylated fatty alcohols may be used alone or in admixture withanionic surfactants, especially the preferred surfactants above. Theaverage chain lengths of the alkyl group R_(ε) in the general formula:R_(ε)O(CH₂CH₂)_(n)His from 6 to 20 carbon atoms. Notably the group R_(ε) may have chainlengths in a range from 9 to 18 carbon atoms.

The average value of n should be at least 2. The numbers of ethyleneoxide residues may be a statistical distribution around the averagevalue. However, as is known, the distribution can be affected by themanufacturing process or altered by fractionation after ethoxylation.Particularly preferred ethoxylated fatty alcohols have a group R_(ε)which has 9 to 18 carbon atoms while n is from 2 to 8.

Also included within this category are nonionic surfactants having aformula:

whereinR_(φ) is a linear alkyl hydrocarbon radical having an average of 6 to 18carbon atoms,R_(γ) and R_(η) are each linear alkyl hydrocarbons of about 1 to about 4carbon atoms,x is an integer of from 1 to 6,y is an integer of from 4 to 20 andz is an integer from 4 to 25.

One preferred nonionic surfactant of the above formula is Poly-TergentSLF-18, a registered trademark of the Olin Corporation, New Haven,Conn., having a composition of the above formula where R_(φ) is a C₆-C₁₀linear alkyl mixture, R_(γ) and R_(η) are methyl, x averages 3, yaverages 12 and z averages 16.

Another preferred nonionic surfactant is:

whereinR_(ι) is a linear, aliphatic hydrocarbon radical having from about 4 toabout 18 carbon atoms including mixtures thereof; andR_(φ) is a linear, aliphatic hydrocarbon radical having from about 2 toabout 26 carbon atoms including mixtures thereof;j is an integer having a value of from 1 to about 3;k is an integer having a value from 5 to about 30; andl is an integer having a value of from 1 to about 3.

Most preferred are compositions in which j is 1, k is from about 10 toabout 20 and l is 1. These surfactants are described in WO 94/22800.Other preferred nonionic surfactants are linear fatty alcoholalkoxylates with a capped terminal group, as described in U.S. Pat. No.4,340,766 to BASF. Particularly preferred is Plurafac LF403 ex. BASF.

Another nonionic surfactant included within this category are compoundsof formula:R_(κ)—(CH₂CH₂O)_(q)H,whereinR_(κ) is a C₆-C₂₄ linear or branched alkyl hydrocarbon radical and q isa number from 2 to 50; more preferably R_(κ) is a C₈-C₁₈ linear alkylmixture and q is a number from 2 to 15.

Polyoxyethylene or polyoxypropylene condensates of alkyl phenols,whether linear- or branched-chain and unsaturated or saturated,containing from about 6 to 12 carbon atoms and incorporating from about2 to about 25 moles of ethylene oxide and/or propylene oxide.

Polyoxyethylene derivatives of sorbitan mono-, di-, and tri-fatty acidesters wherein the fatty acid component has between 12 and 24 carbonatoms. The preferred polyoxyethylene derivatives are of sorbitanmonolaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitantripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitantristearate, sorbitan monooleate, and sorbitan trioleate. Thepolyoxyethylene chains may contain between about 4 and 30 ethylene oxideunits, preferably about 10 to 20. The sorbitan ester derivatives contain1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-,di- or tri-acid esters.

Polyoxyethylene-polyoxypropylene block copolymers having formula:HO(CH₂CH₂O)_(a)(CH(CH₃)CH₂O)_(b)(CH₂CH₂O)_(c)H orHO(CH(CH₃)CH₂O)_(d)(CH₂CH₂O)_(e)(CH(CH₃)CH₂O)_(f)H,whereina, b, c, d, e and f are integers from 1 to 350 reflecting the respectivepolyethylene oxide and polypropylene oxide blocks of said polymer.

The polyoxyethylene component of the block polymer constitutes at leastabout 10% of the block polymer. The material preferably has a molecularweight of between about 1,000 and 15,000, more preferably from about1,500 to about 6,000. These materials are well-known in the art. Theyare available under the trademark “Pluronic” and “Pluronic R”, a productof BASF Corporation.

Amine oxides having formula:R_(λ)R_(μ)R_(ν)N═O,whereinR_(λ), R_(μ), and R_(ν) are saturated aliphatic radicals or substitutedsaturated aliphatic radicals. Preferable amine oxides are those whereinR_(λ) is an alkyl chain of about 10 to about 20 carbon atoms and R_(μ)and R_(ν) are methyl or ethyl groups or both R_(λ) and R_(μ) are alkylchains of about 6 to about 14 carbon atoms and R_(ν) is a methyl orethyl group.Amphoteric Synthetic Detergents

Amphoteric synthetic detergents can be broadly described as derivativesof aliphatic tertiary amines, in which the aliphatic radical may bestraight chain or branched and wherein one of the aliphatic substituentscontain from about 8 to about 18 carbons and one contains an anionicwater-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato orphosphono. Examples of compounds falling within this definition aresodium 3-dodecylamino propionate and sodium 2-dodecylamino propanesulfonate.

Zwitterionic Synthetic Detergents

Zwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium and sulphoniumcompounds in which the aliphatic radical may be straight chained orbranched, and wherein one of the aliphatic substituents contains fromabout 8 to about 18 carbon atoms and one contains an anionicwater-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato orphosphono. These compounds are frequently referred to as betaines.Besides alkyl betaines, alkyl amino and alkyl amido betaines areencompassed within this invention.

Alkyl GlycosidesR_(o)O(R_(π)O)_(n)(Z₁)_(p),whereinR_(o) is a monovalent organic radical (e.g., a monovalent saturatedaliphatic, unsaturated aliphatic or aromatic radical such as alkyl,hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl,hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containingfrom about 6 to about 30 (preferably from about 8 to 18 and morepreferably from about 9 to about 13) carbon atoms;R_(π) is a divalent hydrocarbon radical containing from 2 to about 4carbon atoms such as ethylene, propylene or butylene (most preferablythe unit (R_(π)O)n represents repeating units of ethylene oxide,propylene oxide and/or random or block combinations thereof;n is a number having an average value of from 0 to about 12;Z₁ represents a moiety derived from a reducing saccharide containing 5or 6 carbon atoms (most preferably a glucose unit); andp is a number having an average value of from 0.5 to about 10 preferablyfrom about 0.5 to about 5.

Examples of commercially available materials from HenkelKommanditgesellschaft Aktien of Dusseldorf, Germany include APG 300, 325and 350 with P, being C₉-C₁₁, n is 0 and p is 1.3, 1.6 and 1.8-2.2respectively; APG 500 and 550 with R_(o) is C₁₂-C₁₃, n is 0 and p is 1.3and 1.8-2.2, respectively; and APG 600 with R_(o) being C₁₂-C₁₄, n is 0and p is 1.3.

While esters of glucose are contemplated especially, it is envisagedthat corresponding materials based on other reducing sugars, such asgalactose and mannose are also suitable.

Particularly preferred nonionic surfactants are polyoxyethylene andpolyoxypropylene condensates of linear aliphatic alcohols.

The preferred range of surfactant is from about 0.1 to 40 wt-%, morepreferably from about 0.5 to 15 wt-% of the composition.

Non-ionic surfactants are preferred over anionic surfactants.

The surfactant system preferably comprises weakly foaming non-ionicsurfactants, that serves for the better removal of fat-containingstains, as wetting agents and optionally within the framework of thepreparation of the cleaning formulations as granulation auxiliaries.They may be present in an amount of up to 10 wt-%, based on the totalweight of the hard surface cleaning composition, especially up to 5wt-%, and preferably in the range of from 0.25 wt-% to 4 wt-%.Especially for use in machine dishwashing procedures it is customary touse extremely low-foam compounds. These include especiallyC₁₂-C₂₀alkylpolyethylene glycol-polypropylene glycol ethers each havingup to 15 mol of ethylene oxide and propylene oxide units in themolecule. A particularly preferred non-ionic surfactant is derived froma straight chain fatty alcohol containing from about 16 to about 20carbon atoms (C₁₆-C₂₀ alcohol), preferably a C₁₈alcohol, condensed withan average of from about 6 to about 15 moles, preferably from about 7 toabout 12 moles, and most preferably from about 7 to about 9 moles ofethylene oxide per mole of alcohol. Preferably the ethoxylated nonionicsurfactant so derived has a narrow ethoxylate distribution relative tothe average. Also possible are blends thereof with more sophisticatedsurfactants, such as thepolyoxypropylene/polyoxyethylene/poly-oxypropylene reverse blockpolymers. The PO/EO/PO polymer-type surfactants are well-known to havefoam suppressing or defoaming action, especially in relation to commonfood soil ingredients such as egg.

Highly preferred automatic dishwashing detergent formulations hereinwherein the non-ionic surfactant is present make use of ethoxylatedmonohydroxy alcohol or alkyl phenol and additionally comprise apolyoxyethylene, polyoxypropylene block polymeric compound; theethoxylated monohydroxy alcohol or alkyl phenol fraction of thenon-ionic surfactant comprising from about 20 wt-% to about 80 wt-%,preferably from about 30 wt-% to about 70 wt-%, based on the totalweight of the non-ionic surfactant. Suitable blockpolyoxyethylene-polyoxypropylene polymeric compounds that meet therequirements described hereinbefore include those based on ethyleneglycol, propylene glycol, glycerol, trimethylolpropane andethylenediamine as initiator reactive hydrogen compound. Polymericcompounds made from a sequential ethoxylation and propoxylation ofinitiator compounds with a single reactive hydrogen atom, such asC₁₂-C₁₈ aliphatic alcohols, do not generally provide satisfactory sudscontrol in the instant automatic dishwashing detergent formulations.

It is also possible, however, to use other known low-foam non-ionicsurfactants, for example C₁₂-C₁₈alkylpolyethylene glycol-polybutyleneglycol ethers each having up to 8 mol of ethylene oxide and butyleneoxide units in the molecule, end-group-terminated alkylpolyalkyleneglycol mixed ethers, and also the foaming but ecologically attractiveC₈-C₁₄alkylpolyglucosides having a degree of polymerisation ofapproximately from 1 to 4 and/or C₁₂-C₁₄alkylpolyethylene glycols havingfrom 3 to 8 ethylene oxide units in the molecule. Also suitable aresurfactants from the glucamide family, e.g. alkyl-N-methyl-glucamides inwhich the alkyl moiety preferably consists of a fatty alcohol having acarbon chain length of C₆-C₁₄. In some cases it is advantageous for thedescribed surfactants to be used in the form of mixtures, for example acombination of alkylpolyglycoside with fatty alcohol ethoxylates or ofglucamide with alkylpolyglycosides. Preferred compositions of thepresent invention can optionally comprise limited quantities (up toabout 2%) of nitrogen-containing nonionic surfactants, such asalkyldimethyl amineoxides or fatty glucosamides; when present, suchsurfactants normally require suds suppression e.g., by silicone sudssuppressors.

In addition to the bleach catalysts according to formulae (1) and/or(1′) it is also possible to use further known transition metal salts orcomplexes known as bleach-activating active ingredients and/orconventional bleach activators, that is to say compounds that, underperhydrolysis conditions, yield unsubstituted or substituted perbenzo-and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms,especially from 2 to 4 carbon atoms. Suitable bleach activators includethe customary bleach activators, mentioned at the beginning, that carryO- and/or N-acyl groups having the indicated number of carbon atomsand/or unsubstituted or substituted benzoyl groups. Preference is givento polyacylated alkylenediamines, especially tetraacetylethylenediamine(TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU),N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives,especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated phenylsulfonates, especially nonanoyloxybenzenesulfonate (NOBS)or isononanoyloxybenzenesulfonate, acylated polyvalent alcohols,especially triacetin, ethylene glycol diacetate and2,5-di-acetoxy-2,5-dihydrofuran, and also acetylated sorbitol andmannitol and acylated sugar derivatives, especially pentaacetylglucose(PAG), sucrose polyacetate (SUPA), pentaacetylfructose,tetraacetylxylose and octaacetyllactose as well as acetylated,optionally N-alkylated glucamine and gluconolactone. It is also possibleto use the combinations of conventional bleach activators known fromGerman Patent Application DE-A-4443177.

The cleaning formulations according to the invention may also containorganic peroxides, especially diacyl peroxides. Nonlimiting examples ofdiacyl peroxides useful herein include dibenzoyl peroxide, lauroylperoxide, and dicumyl peroxide.

The low-alkalinity machine dishwashing formulations according to theinvention preferably comprise the customary alkaline carriers, forexample alkali silicates, alkali carbonates and/or alkali hydrogencarbonates. The alkaline carrier are selected so that when the detergentis dissolved in water at a concentration of 1-10 g/L, the pH remains inthe range of above about 8, preferably from about 9.0 to about 11. Thealkaline carriers customarily used include alkali carbonates, hydrogencarbonates and alkali silicates having a molar ratio SiO₂/M₂O (M=alkalimetal atom) of from 1:1 to 2.5:1, sodium borate, sodium hydroxide ormixtures thereof. The amount of the alkaline carrier in the instantautomatic dishwashing detergent compositions is preferably from about 1wt-% to about 50 wt-%, based on the total weight of the formulation. Ina preferred embodiment, the alkaline carrier is present in the automaticdishwashing detergent formulation in an amount from about 5 wt-% toabout 40 wt-%, preferably from about 10 wt-% to about 30 wt-%, based onthe total weight of the formulation. An alkaline carrier systempreferably used in the formulations according to the invention is amixture of carbonate and hydrogen carbonate, preferably sodium carbonateand hydrogen carbonate, which mixture is present in an amount of up to60 wt-%, preferably from 10 wt-% to 40 wt-%, based on the total weightof the formulation. Depending upon the pH value ultimately desired, theratio of carbonate used to hydrogen carbonate used will vary, butusually an excess of sodium hydrogen carbonate is used, so that theratio by weight of hydrogen carbonate to carbonate is generally from 1:1to 15:1.

Alkali silicates can be present in amounts of up to 30 wt-%, based onthe total weight of the formulation. It is preferable to dispensealtogether with the use of the highly alkaline metasilicates as alkalinecarriers. When present, sodium and potassium, especially sodium,silicates are preferred. Particularly preferred alkali metal silicatesare granular hydrous sodium silicates having SiO₂:Na₂O ratio of about2.0 or about 2.4. Most preferred is a granular hydrous sodium silicatehaving a SiO₂:Na₂O ratio of 2.0.

In a further preferred embodiment, the hard surface cleaningcompositions according to the invention contain from 20 wt-% to 40 wt-%water-soluble organic builder, especially alkali citrate, from 5 wt-% to15 wt-% alkali carbonate and from 20 wt-% to 40 wt-% alkali silicatebased on the total weight of the formulation.

The present hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations, may contain one or more corrosion inhibitors oranti-tarnish aids. Such materials are preferred components of machinedishwashing compositions especially in certain European countries wherethe use of electroplated nickel silver and sterling silver is stillcomparatively common in domestic flatware, or when aluminium protectionis a concern and the composition is low in silicate. When present, suchprotecting materials are preferably incorporated at low levels, e.g.,from about 0.01 wt-% to about 5 wt-%, based on the total weight of theformulation, preferably dishwashing detergent formulation, morepreferably automatic dishwashing detergent formulation. Suitablecorrosion inhibitors include paraffin oil, unsubstituted or substitutedbenzotriazole and comparable compounds; mercaptans or thiols includingthionaphtol and thioanthranol; divalent phenols, trivalent phenols,Aluminium fatty acid salts, such as aluminium tristearate, andmanganese, titanium, zirconium, hafnium, vanadium, cobalt or ceriumsalts and/or complexes, in which the said metals are present in one ofoxidation states II, III, IV, V and VI. The formulator will recognizethat such materials will generally be used judiciously and in limitedquantities so as to avoid any tendency to produce spots or films onglassware or to compromise the bleaching action of the compositions.Suitable Corrosion inhibitors are disclosed in U.S. Pat. No. 5,480,576,GB2297096, EP636688, GB2283494 and EP 690122.

In addition, the formulations according to the invention may compriseenzymes, such as proteases, amylases, pullulanases, cutinases andlipases, for example proteases such as BLAP®, Optimase®, Opticlean®,Maxacal®, Maxapem®, Esperase® and/or Savinase®, amylases such asTermamyl®, Amylase-LT®, Maxamyl® and/or Duramyl®, lipases such asLipolase®, Lipomax®, Lumafast® and/or Lipozym®. The enzymes which may beused can, as described e.g. in International Patent Applications WO92/11347 and WO 94/23005, be adsorbed on carriers and/or embedded inencapsulating substances in order to safeguard them against prematureinactivation. They are present in the cleaning formulations according tothe invention preferably in amounts not exceeding 5 wt-%, especially inamounts of from 0.1 wt-% to 1.2 wt-%, based on the total weight of theformulation.

Amylases: The present invention preferably makes use of amylases havingimproved stability in detergents, especially improved oxidativestability. Such amylases are non-limitingly illustrated by thefollowing: (a) An amylase according to WO 94/02597, Novo Nordisk A/S,published Feb. 3, 1994, as further illustrated by a mutant in whichsubstitution is made, using alanine or threonine (preferably threonine),of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TERMAMYL®, or the homologousposition variation of a similar parent amylase, such as B.amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b)Stability-enhanced amylases as described by Genencor International in apaper entitled “Oxidatively Resistant alpha-Amylases” presented at the207th American Chemical Society National Meeting, Mar. 13-17, 1994, byC. Mitchinson. Therein it was noted that bleaches in automaticdishwashing detergents inactivate alpha-amylases but that improvedoxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Any other oxidative stability-enhanced amylasecan be used.

Proteases: Protease enzymes are usually present in preferred embodimentsof the invention at levels between 0.001 wt-% and 5 wt-%, based on thetotal weight of the formulation. The proteolytic enzyme can be ofanimal, vegetable or microorganism (preferred) origin. More preferred isserine proteolytic enzyme of bacterial origin. Purified or nonpurifiedforms of enzyme may be used. Proteolytic enzymes produced by chemicallyor genetically modified mutants are included by definition, as are closestructural enzyme variants. Suitable commercial proteolytic enzymesinclude Alcalase®, Esperase®, Durazyme®, Savinase®, Maxatase®, Maxacal®,and Maxapem® 15 (protein engineered Maxacal). Purafect® and subtilisingBPN and BPN′ are also commercially available.

When present, lipases comprise from about 0.001 wt-% to about 0.01 wt-%,based on the total weight of the formulation and are optionally combinedwith from about 1 wt-% to about 5 wt-% of a surfactant havinglimesoap-dispersing properties, such as an alkyldimethylamine N-oxide ora sulfobetaine. Suitable lipases for use herein include those ofbacterial, animal and fungal origin, including those from chemically orgenetically modified mutants. When incorporating lipases into theinstant compositions, their stability and effectiveness may in certaininstances be enhanced by combining them with small amounts (e.g., lessthan 0.5 wt-% of the composition) of oily but non-hydrolyzing materials.

The enzyme-containing hard surface cleaning compositions, preferablydishwashing detergent formulations, more preferably automaticdishwashing detergent formulations herein may optionally also comprisefrom about 0.001% to about 10%, preferably from about 0.005% to about8%, most preferably from about 0.01% to about 6%, by weight of an enzymestabilizing system. The enzyme stabilizing system can be any stabilizingsystem which is compatible with the detersive enzyme. Such a system maybe inherently provided by other formulation actives, or be addedseparately, e.g., by the formulator or by a manufacturer ofdetergent-ready enzymes. Such stabilizing systems can, for example,comprise calcium ion, boric acid, propylene glycol, short chaincarboxylic acids, boronic acids, and mixtures thereof, and are designedto address different stabilization problems depending on the type andphysical form of the detergent composition.

One stabilizing approach is the use of water-soluble sources of calciumand/or magnesium ions in the finished compositions which provide suchions to the enzymes. Calcium ions are generally more effective thanmagnesium ions and are preferred herein if only one type of cation isbeing used. Typical detergent compositions, especially liquids, willcomprise from about 1 to about 30, preferably from about 2 to about 20,more preferably from about 8 to about 12 millimoles of calcium ion perlitre of finished detergent composition, though variation is possibledepending on factors including the multiplicity, type and levels ofenzymes incorporated. Preferably water-soluble calcium or magnesiumsalts are employed, including for example calcium chloride, calciumhydroxide, calcium formate, calcium malate, calcium maleate, calciumhydroxide and calcium acetate; more generally, calcium sulfate ormagnesium salts corresponding to the exemplified calcium salts may beused. Further increased levels of Calcium and/or Magnesium may of coursebe useful, for example for promoting the grease-cutting action ofcertain types of surfactant.

Another stabilizing approach is by use of borate species. See Severson,U.S. Pat. No. 4,537,706. Borate stabilizers, when used, may be at levelsof up to 10 wt-% or more of the composition though more typically,levels of up to about 3 wt-% of boric acid or other borate compoundssuch as borax or orthoborate are suitable for liquid detergent use.Substituted boric acids such as phenylboronic acid, butaneboronic acid,p-bromophenylboronic acid or the like can be used in place of boric acidand reduced levels of total boron in detergent compositions may bepossible though the use of such substituted boron derivatives.Stabilizing systems of certain hard surface cleaning compositions, forexample automatic dishwashing compositions, may further comprise from 0to about 10 wt-%, preferably from about 0.01 wt-% to about 6 wt-%, ofchlorine bleach scavengers, added to prevent chlorine bleach speciespresent in many water supplies from attacking and inactivating theenzymes, especially under alkaline conditions. While chlorine levels inwater may be small, typically in the range from about 0.5 ppm to about1.75 ppm, the available chlorine in the total volume of water that comesin contact with the enzyme, for example during dish- or fabric-washing,can be relatively large; accordingly, enzyme stability to chlorinein-use is sometimes problematic. Since perborate or percarbonate, whichhave the ability to react with chlorine bleach, may present in certainof the instant compositions in amounts accounted for separately from thestabilizing system, the use of additional stabilizers against chlorine,may, most generally, not be essential, though improved results may beobtainable from their use. Suitable chlorine scavenger anions are widelyknown and readily available, and, if used, can be salts containingammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate,iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organicamines such as ethylenediamine-tetracetic acid (EDTA) or alkali metalsalt thereof, monoethanolamine (MEA), and mixtures thereof can likewisebe used. Likewise, special enzyme inhibition systems can be incorporatedsuch that different enzymes have maximum compatibility. Otherconventional scavengers such as bisulfate, nitrate, chloride, sources ofhydrogen peroxide such as sodium perborate tetrahydrate, sodiumperborate monohydrate and sodium percarbonate, as well as phosphate,condensed phosphate, acetate, benzoate, citrate, formate, lactate,malate, tartrate, salicylate, etc., and mixtures thereof can be used ifdesired. In general, since the chlorine scavenger function can beperformed by ingredients separately listed under better recognizedfunctions, (e.g., hydrogen peroxide sources), there is no absoluterequirement to add a separate chlorine scavenger unless a compoundperforming that function to the desired extent is absent from anenzyme-containing embodiment of the invention; even then, the scavengeris added only for optimum results. Moreover, the formulator willexercise a chemist's normal skill in avoiding the use of any enzymescavenger or stabilizer which is majorly incompatible, as formulated,with other reactive ingredients. In relation to the use of ammoniumsalts, such salts can be simply admixed with the detergent compositionbut are prone to adsorb water and/or liberate ammonia during storage.Accordingly, such materials, if present, are desirably protected in aparticle such as that described in U.S. Pat. No. 4,652,392.

Peroxidase enzymes are optionally useful in the present invention. Theyare used for “solution bleaching,” i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.

The t hard surface cleaning compositions, preferably dishwashingdetergent formulation, more preferably automatic dishwashing detergentformulation of the invention can optionally contain foam suppressors,for example alkyl phosphate ester suds suppressor, silicone sudssuppressor, or combinations thereof. Levels in general are from 0 wt-%to about 10 wt-%, preferably, from about 0.001 wt-% to about 5 wt-%,based on the total weight of the formulation. Typical levels tend to below, e.g., from about 0.01 wt-% to about 3 wt-% when a silicone sudssuppressor is used. Preferred non-phosphate compositions omit thephosphate ester component entirely.

Highly preferred silicone suds suppressors are the compounded typesknown for use in laundry detergents such as heavy-duty granules,although types hitherto used only in heavy-duty liquid detergents mayalso be incorporated in the instant compositions. For example,polydimethylsiloxanes having trimethylsilyl or alternate endblockingunits may be used as the silicone. These may be compounded with silicaand/or with surface-active nonsilicon components, as illustrated by asuds suppressor comprising 12 wt-% silicone/silica, 18 wt-% stearylalcohol and 70 wt-% starch in granular form.

Preferred alkyl phosphate esters contain from 16-20 carbon atoms. Highlypreferred alkyl phosphate esters are monostearyl acid phosphate ormonooleyl acid phosphate, or salts thereof, particularly alkali metalsalts, or mixtures thereof.

It has been found preferable to avoid the use of simplecalcium-precipitating soaps as antifoams in the present compositions asthey tend to deposit on the dishware. Indeed, phosphate esters are notentirely free of such problems and the formulator will generally chooseto minimize the content of potentially depositing antifoams in theinstant compositions.

Other examples for foam suppressors are paraffin, paraffin/alcoholcombinations, or bisfatty acid amides.

The hard surface cleaning compositions, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations herein may also optionally contain one or more heavy metalchelating agents, such as hydroxyethyldiphosphonate, (HEDP). Moregenerally, chelating agents suitable for use herein can be selected fromthe group consisting of amino carboxylates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturesthereof. Other suitable chelating agents for use herein are thecommercial DEQUEST series, and chelants from Nalco, Inc.

Aminocarboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts thereof and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in thecompositions of the invention when at least low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates). Preferably, theseaminophosphonates do not contain alkyl or alkenyl groups with more thanabout 6 carbon atoms.

A highly preferred biodegradable chelator for use herein isethylenediamine disuccinate (“EDDS”).

If utilized, these chelating agents or transition-metal selectivesequestrants will generally comprise from about 0.001 wt-% to about 10wt-%, more preferably from about 0.05 wt-% to about 1 wt-%, based on thetotal weight of the formulation, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations herein.

Preferred hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations herein may additionally contain a dispersant polymer. Whenpresent, a dispersant polymer is typically at levels in the range from 0wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 20 wt-%,more preferably from about 1 wt-% to about 8 wt-%, based on the totalweight of the formulation. Dispersant polymers are useful for improvedfilming performance of the present dishwasher detergent compositions,especially in higher pH embodiments, such as those in which wash pHexceeds about 9.5. Particularly preferred are polymers, which inhibitthe deposition of calcium carbonate or magnesium silicate on dishware.

Suitable polymers are preferably at least partially neutralized oralkali metal, ammonium or substituted ammonium (e.g., mono-, di- ortriethanolammonium) salts of polycarboxylic acids. The alkali metal,especially sodium salts are most preferred. While the molecular weightof the polymer can vary over a wide range, it preferably is from about1,000 to about 500,000, more preferably is from about 1,000 to about250,000.

Unsaturated monomeric acids that can be polymerized to form suitabledispersant polymers include acrylic acid, maleic acid (or maleicanhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid,citraconic acid and methylenemalonic acid. The presence of monomericsegments containing no carboxylate radicals such as methyl vinyl ether,styrene, ethylene, etc. is suitable provided that such segments do notconstitute more than about 50 wt-% by weight of the dispersant polymer.

Copolymers of acrylamide and acrylate having a molecular weight of fromabout 3,000 to about 100,000, preferably from about 4,000 to about20,000, and an acrylamide content of less than about 50 wt-%, preferablyless than about 20 wt-%, by weight of the dispersant polymer can also beused. Most preferably, such dispersant polymer has a molecular weight offrom about 4,000 to about 20,000 and an acrylamide content of from about0 wt-% to about 15 wt-%, based on the total weight of the polymer.

Particularly preferred dispersant polymers are low molecular weightmodified polyacrylate copolymers. Such copolymers contain as monomerunits: a) from about 90 wt-% to about 10 wt-%, preferably from about 80wt-% to about 20 wt-% acrylic acid or its salts and b) from about 10wt-% to about 90 wt-%, preferably from about 20 wt-% to about 80 wt-% ofa substituted acrylic monomer or its salt and have the general formula:—[(C(R_(a))C(R_(b))(C(O)OR_(c))] wherein the apparently unfilledvalencies are in fact occupied by hydrogen and at least one of thesubstituents R_(a), R_(b), or R_(c), preferably R_(a) or R_(b), is a 1to 4 carbon alkyl or hydroxyalkyl group; R_(a) or R_(b) can be ahydrogen and R_(c) can be a hydrogen or alkali metal salt. Mostpreferred is a substituted acrylic monomer wherein R_(a) is methyl,R_(b) is hydrogen, and R_(c) is sodium.

Suitable low molecular weight polyacrylate dispersant polymer preferablyhas a molecular weight of less than about 15,000, preferably from about500 to about 10,000, most preferably from about 1,000 to about 5,000.The most preferred polyacrylate copolymer for use herein has a molecularweight of about 3,500 and is the fully neutralized form of the polymercomprising about 70 wt-% acrylic acid and about 30 wt-% methacrylicacid.

Other dispersant polymers useful herein include the polyethylene glycolsand polypropylene glycols having a molecular weight of from about 950 toabout 30,000.

Yet other dispersant polymers useful herein include the cellulosesulfate esters such as cellulose acetate sulfate, cellulose sulfate,hydroxyethyl cellulose sulfate, methylcellulose sulfate, andhydroxypropylcellulose sulfate. Sodium cellulose sulfate is the mostpreferred polymer of this group.

Other suitable dispersant polymers are the carboxylated polysaccharides,particularly starches, celluloses and alginates.

Yet another group of acceptable dispersants are the organic dispersantpolymers, such as polyaspartate.

Depending on whether a greater or lesser degree of compactness isrequired, filler materials can also be present in the instant hardsurface cleaning compositions, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations. These include sucrose, sucrose esters, sodium sulfate,potassium sulfate, etc., in amounts up to about 70 wt-%, preferably from0 wt-% to about 40 wt-%, based on the total weight of the formulation,preferably dishwashing detergent formulations, more preferably automaticdishwashing detergent formulations. Preferred filler is sodium sulfate,especially in good grades having at most low levels of trace impurities.

Sodium sulfate used herein preferably has a purity sufficient to ensureit is non-reactive with bleach; it may also be treated with low levelsof sequestrants, such as phosphonates or EDDS in magnesium-salt form.Note that preferences, in terms of purity sufficient to avoiddecomposing bleach, applies also to pH-adjusting component ingredients,specifically including any silicates used herein.

Organic solvents that can be used in the cleaning formulations accordingto the invention, especially when the latter are in liquid or pasteform, include alcohols having from 1 to 4 carbon atoms, especiallymethanol, ethanol, isopropanol and tert-butanol, diols having from 2 to4 carbon atoms, especially ethylene glycol and propylene glycol, andmixtures thereof, and the ethers derivable from the mentioned classes ofcompound. Such water-miscible solvents are present in the cleaningformulations according to the invention preferably in amounts notexceeding 20 wt-%, especially in amounts of from 1 wt-% to 15 wt-%,based on the total weight of the formulation.

Many hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations herein will be buffered, i.e., they are relativelyresistant to pH drop in the presence of acidic soils. However, othercompositions herein may have exceptionally low buffering capacity, ormay be substantially unbuffered. Techniques for controlling or varyingpH at recommended usage levels more generally include the use of notonly buffers, but also additional alkalis, acids, pH-jump systems, dualcompartment containers, etc., and are well known to those skilled in theart. Certain hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations, comprise a pH-adjusting component selected fromwater-soluble alkaline inorganic salts and water-soluble organic orinorganic builders. The pH-adjusting components are selected so thatwhen the hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations is dissolved in water at a concentration of 1,000-5,000ppm, the pH remains in the range of above about 8, preferably from about9.5 to about 11. The preferred nonphosphate pH-adjusting component canbe selected from the group consisting of:

-   (i) sodium carbonate or sesquicarbonate;-   (ii) sodium silicate, preferably hydrous sodium silicate having    SiO₂:Na₂O ratio of from about 1:1 to about 2:1, and mixtures thereof    with limited quantities of sodium metasilicate;-   (iii) sodium citrate;-   (iv) citric acid;-   (v) sodium bicarbonate;-   (vi) sodium borate, preferably borax;-   (vii) sodium hydroxide; and-   (viii) mixtures of (i)-(vii).

Preferred embodiments contain low levels of silicate (i.e. from about 3%to about 10% SiO₂). Illustrative of highly preferred pH-adjustingcomponent systems of this specialized type are binary mixtures ofgranular sodium citrate with anhydrous sodium carbonate, andthree-component mixtures of granular sodium citrate trihydrate, citricacid monohydrate and anhydrous sodium carbonate.

The amount of the pH adjusting component in compositions used forautomatic dishwashing is preferably from about 1 wt-% to about 50 wt-%,based on the total weight of the formulation. In a preferred embodiment,the pH-adjusting component is present in the composition in an amountfrom about 5 wt-% to about 40 wt-%, preferably from about 10 wt-% toabout 30 wt-%, based on the total weight of the formulation.

For compositions herein having a pH between about 9.5 and about 11 ofthe initial wash solution, particularly preferred automatic dishwashingdetergent formulations embodiments comprise, by weight of the automaticdishwashing detergent formulations, from about 5 wt-% to about 40 wt-%,preferably from about 10 wt-% to about 30 wt-%, most preferably fromabout 15 wt-% to about 20 wt-%, of sodium citrate with from about 5 wt-%to about 30 wt-%, preferably from about 7 wt-% to 25 wt-%, mostpreferably from about 8 wt-% to about 20 wt-% sodium carbonate.

The essential pH-adjusting system can be complemented (i.e. for improvedsequestration in hard water) by other optional detergency builder saltsselected from nonphosphate detergency builders known in the art, whichinclude the various water-soluble, alkali metal, ammonium or substitutedammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates.Preferred are the alkali metal, especially sodium, salts of suchmaterials. Alternate water-soluble, non-phosphorus organic builders canbe used for their sequestering properties. Examples of polyacetate andpolycarboxylate builders are the sodium, potassium, lithium, ammoniumand substituted ammonium salts of ethylenediamine tetraacetic acid;nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinicacid, oxydisuccinic acid, carboxymethoxysuccinic acid, mellitic acid,and sodium benzene polycarboxylate salts. Automatic dishwashingdetergent compositions may further comprise water-soluble silicates.Water-soluble silicates herein are any silicates which are soluble tothe extent that they do not adversely affect spotting/filmingcharacteristics of the automatic dishwashing detergent formulationscomposition.

Examples of silicates are sodium metasilicate and, more generally, thealkali metal silicates, particularly those having a SiO₂:Na₂O ratio inthe range 1.6:1 to 3.2:1; and layered silicates, such as the layeredsodium silicates described in U.S. Pat. No. 4,664,839, issued May 12,1987 to H. P. Rieck. NaSKS-6® is a crystalline layered silicate marketedby Hoechst (commonly abbreviated herein as “SKS-6”). Unlike zeolitebuilders, Na SKS-6 and other water-soluble silicates useful herein donot contain aluminum. NaSKS-6 is the δ-Na₂SiO₅ form of layered silicateand can be prepared by methods such as those described in GermanDE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a preferred layered silicatefor use herein, but other such layered silicates, such as those havingthe general formula NaMSi_(x)O_(2x+1).yH2O wherein M is sodium orhydrogen, x is a number from 1.9 to 4, preferably 2, and y is a numberfrom 0 to 20, preferably 0 can be used. Various other layered silicatesfrom Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the α, β- andγ-forms. Other silicates may also be useful, such as for examplemagnesium silicate, which can serve as a crispening agent in granularformulations, as a stabilizing agent for oxygen bleaches, and as acomponent of suds control systems.

Silicates particularly useful in hard surface cleaning compositions,preferably dishwashing detergent formulations, more preferably automaticdishwashing detergent formulations applications include granular hydrous2-ratio silicates such as BRITESIL® H20 from PQ Corp., and the commonlysourced BRITESIL® H24 though liquid grades of various silicates can beused when the automatic dishwasher composition has liquid form. Withinsafe limits, sodium metasilicate or sodium hydroxide alone or incombination with other silicates may be used in an automatic dishwashercontext to boost wash pH to a desired level.

Hydrotrope materials such as sodium benzene sulfonate, sodium toluenesulfonate, sodium cumene sulfonate, etc., can be present, e.g., forbetter dispersing surfactant.

Bleach-stable perfumes (stable as to odor); and bleach-stable dyes canalso be added to the present compositions in appropriate amounts. Othercommon detergent ingredients consistent with the spirit and scope of thepresent invention are not excluded.

Since hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations compositions herein can contain water-sensitive ingredientsor ingredients which can co-react when brought together in an aqueousenvironment, it is desirable to keep the free moisture content of thehard surface cleaning compositions, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations at a minimum, e.g., 7 wt-% or less, preferably 4 wt-% orless of the hard surface cleaning compositions, preferably dishwashingdetergent formulations, more preferably automatic dishwashing detergentformulations; and to provide packaging which is substantiallyimpermeable to water and carbon dioxide. Coating measures may be used toprotect the ingredients from each other and from air and moisture.

The hard surface cleaning compositions, preferably dishwashing detergentformulations, more preferably automatic dishwashing detergentformulations according to the present invention may also comprise atleast one organic peroxy acid.

As organic peroxy acid any known peroxy acid can be used. For example,mono- or poly-peroxy acids having at least 1 carbon atoms, preferablyfrom 1 to 20 carbon atoms, in the alkyl chain. It is also possible touse the corresponding precursor of these acids.

Preferred are organic peroxy acids of formula

whereinM signifies hydrogen or a cation,R_(d) signifies unsubstituted C₁-C₁₈alkyl; substituted C₁-C₁₈alkyl;unsubstituted aryl; substituted aryl; —(C₁-C₆alkylene)-aryl, wherein thealkylene and/or the alkyl group may be substituted; andphthalimidoC₁-C₈alkylene, wherein the phthalimido and/or the alkylenegroup may be substituted.

The C₁-C₁₈alkyl radicals mentioned are generally, for example,straight-chain or branched alkyl radicals, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl orstraight-chain or branched pentyl, hexyl, heptyl or octyl.

Preference is given to C₁-C₁₂alkyl radicals, especially C₁-C₈alkylradicals and preferably C₁-C₄alkyl radicals. The mentioned alkylradicals may be unsubstituted or substituted e.g. by hydroxy,C₁-C₄alkoxy, sulfo or by sulfato.

The corresponding unsubstituted alkyl radicals are preferred. Veryspecial preference is given to methyl and ethyl, especially methyl.

Examples of aryl radicals that generally come into consideration arephenyl or naphthyl each unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino,N-mono- or N,N-di-C₁-C₄alkylamino unsubstituted or substituted byhydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl,phenoxy or by naphthyloxy. Preferred substituents are C₁-C₄alkyl,C₁-C₄alkoxy, phenyl and hydroxy.

The C₁-C₆alkylene groups mentioned are, for example, straight-chain orbranched alkylene radicals, such as methylene, ethylene, n-propylene orn-butylene. C₁-C₄alkylene groups are preferred. The alkylene radicalsmentioned may be unsubstituted or substituted, for example by hydroxy orC₁-C₄alkoxy.

The cation M can be any suitable cation or mixtures of cations. Examplesof cations that generally come into consideration are alkali metalcations, such as lithium, potassium and especially sodium, alkalineearth metal cations, such as magnesium and calcium, and ammoniumcations. The alkali metal cations, especially sodium, are preferred.

Very preferred organic peroxy acids and their salts are those of formula

whereinM signifies hydrogen or an alkali metal, andR′^(d) signifies unsubstituted C₁-C₄alkyl; phenyl; —C₁-C₂alkylene-phenylor phthalimidoC₁-C₈alkylene.

Especially preferred is CH₃COOOH and its alkali salts.

Especially preferred is also e-phthalimido peroxy hexanoic acid and itsalkali salts.

Instead of the peroxy acid it is also possible to use organic peroxyacid precursors and H₂O₂. Such precursors are the correspondingcarboxyacid or the corresponding carboxyanhydrid or the correspondingcarbonylchlorid, or amides, or esters, which can form the peroxy acidson perhydrolysis. Such reactions are commonly known.

The preparation of the solid formulations according to the invention isproblem-free and can be carried out in a manner known in principle, forexample by spray-drying or granulation, peroxy compound and bleachcatalyst optionally being added separately at a later stage.

Cleaning formulations according to the invention in the form of aqueoussolutions or solutions containing some other customary solvent areproduced especially advantageously by simply mixing together theingredients, which can be introduced into an automatic mixer as such orin the form of a solution.

The formulation according to the invention may take the form of acomplete dishwashing detergent or in the alternative may take the formof a separate bleaching additive. In the latter case the bleachingadditive may used for removing coloured stains on crockery/kitchenwarein a separate liquor before the items are washed in a dishwasher. Thebleaching additive can also be used in a liquor together with either ableach-free washing agent or a bleach-containing washing agent as ableach booster.

The dishwasher detergent formulations can take a variety of physicalforms such as, for example, powder, granule, tablets (tabs) and liquid.

When a liquid formulation is used, the formulation may comprise athickener, such as is commonly used to increase the viscosity of theformulation and appeal to the consumer. Preferred examples of suchthickeners include Xantham gum, cellulose derivatives and polyacrylicacid derivatives.

The formulations according to the invention are preferably in the formof powder-form, granular or tablet-form preparations which can beproduced in a manner known per se, for example by mixing, granulating,roller-compacting and/or by spray-drying those components which are ableto withstand thermal stress and then mixing in the more sensitivecomponents, which include especially enzymes, bleaching agents and thebleach catalyst.

The advantages of tablets reside in the ease of dispensing andconvenience in handling. Tablets are the most compact form of soliddetergent formulation and usually have a volumetric density of, forexample, from 0.9 to 1.3 kg/litre. To achieve rapid dissolution, suchtablets may contain special dissolution aids:

-   -   carbonate/hydrogen carbonate/citric acid as effervescents;    -   disintegrators, such as cellulose, carboxymethyl cellulose or        cross-linked poly(N-vinyl-pyrrolidone);    -   rapidly dissolving materials, such as sodium (potassium)        acetates, or sodium (potassium) citrates;    -   rapidly dissolving, water-soluble, rigid coating agents, such as        dicarboxylic acids.

The tablets may also comprise combinations of such dissolution aids.

A tablet may include a tabletting aid such as polyethyleneglycol.

For the preparation of the cleaning formulations according to theinvention in tablet-form, the procedure is preferably as follows: allthe constituents are mixed together in a mixer and the mixture iscompressed by means of conventional tabletting presses, for exampleeccentric tablet presses or rotary tablet presses, at compressionpressures in the range of from 200·10⁵ Pa to 1500·10⁵ Pa. There are thusobtained in a problem-free manner tablets that are resistant to breakingbut nevertheless dissolve sufficiently rapidly under use conditions andhave a flexural strength usually exceeding 150 N. A tablet so producedpreferably has a weight of from 15 g to 40 g, especially from 20 g to 30g, at a diameter of from 35 mm to 40 mm.

Tablets can also be prepared in the form of twin or multi layer tablets.This allows a separation of sensitive compounds from each other (e.g.bleach from enzymes, or persalts from catalysts) thereby stabilizing theformulation.

The preparation of the formulations according to the invention in theform of non-dusty, storage-stable pourable powders and/or granuleshaving high bulk densities in the range of from 800 to 1000 g/l can becarried out by, in a first process step, mixing the builder componentswith at least some of the liquid mixing components, thus increasing thebulk density of the resulting premix, and subsequently—if desired afterintermediate drying—combining the other constituents of the formulation,including the bleach catalyst, with the premix so obtained.

The invention relates also to granules that comprise the catalystsaccording to the invention and are suitable for incorporation into apowder-form, granular or tablet-form dishwashing detergent. Suchgranules preferably comprise:

-   a) from 1 to 99 wt-%, preferably from 1 to 40 wt-%, and especially    from 1 to 30 wt-%, of at least one metal complex compound of    formula (1) and/or (1′),-   b) from 1 to 99 wt-%, preferably from 10 to 99 wt-%, and especially    from 20 to 80 wt-%, of at least one binder,-   c) from 0 to 20 wt-%, especially from 1 to 20 wt-%, of at least one    encapsulating material,-   d) from 0 to 20 wt-% of at least further additive and-   e) from 0 to 20 wt-% of water.

As binder (b) there come into consideration water-soluble, dispersibleor water-emulsifiable anionic dispersants, non-ionic dispersants,polymers and waxes.

The anionic dispersants used are, for example, commercially availablewater-soluble anionic dispersants for dyes, pigments etc.

The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated diphenyls or diphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerisedorganic sulfonic acids, sodium salts of polymerisedalkylnaphthalenesulfonic acids, sodium salts of polymerisedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acid,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalenemethane-sulfonates, lignosulfonates or oxylignosulfonatesand heterocyclic polysulfonic acids. Especially suitable anionicdispersants are condensation products of naphthalenesulfonic acids withformaldehyde, sodium salts of polymerised organic sulfonic acids,(mono-/di-)-alkylnaphthalenesulfonates, polyalkylated polynucleararylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid,lignosulfonates, oxylignosulfonates and condensation products ofnaphthalenesulfonic acid with a polychloromethyldiphenyl.

Suitable non-ionic dispersants are especially compounds having a meltingpoint of, preferably, at least 35° C. that are emulsifiable, dispersibleor soluble in water, for example the following compounds:

-   1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl    alcohol;-   2. addition products of, preferably, from 2 to 80 mol of alkylene    oxide, especially ethylene oxide, wherein some of the ethylene oxide    units may have been replaced by substituted epoxides, such as    styrene oxide and/or propylene oxide, with higher unsaturated or    saturated monoalcohols, fatty acids, fatty amines or fatty amides    having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl    phenols, benzyl phenols or alkyl phenols, the alkyl radicals of    which have at least 4 carbon atoms;-   3. alkylene oxide, especially propylene oxide, condensation products    (block polymers);-   4. ethylene oxide/propylene oxide adducts with diamines, especially    ethylenediamine;-   5. reaction products of a fatty acid having from 8 to 22 carbon    atoms and a primary or secondary amine having at least one    hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene    oxide addition products of such hydroxyalkyl-group-containing    reaction products;-   6. sorbitan esters, preferably having long-chain ester groups, or    ethoxylated sorbitan esters, such as polyoxyethylene sorbitan    monolaurate having from 4 to 10 ethylene oxide units or    polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene    oxide units;-   7. addition products of propylene oxide with a tri- to hexa-hydric    aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or    pentaerythritol; and-   8. fatty alcohol polyglycol mixed ethers, especially addition    products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol    of propylene oxide with aliphatic monoalcohols having from 8 to 22    carbon atoms.    Especially suitable non-ionic dispersants are surfactants of formula    R₂₃—O-(alkylene-O)_(n)—R₂₄  (9),    wherein-   R₂₃ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl;-   R₂₄ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at    least 6 carbon atoms; or benzyl;-   “alkylene” is an alkylene radical having from 2 to 4 carbon atoms    and-   n is a number from 1 to 60.

The substituents R₂₃ and R₂₄ in formula (9) are advantageously each thehydrocarbon radical of an unsaturated or, preferably, saturatedaliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbonradical may be straight-chain or branched.

R₂₃ and R₂₄ are preferably each independently of the other an alkylradical having from 9 to 14 carbon atoms.

Aliphatic saturated monoalcohols that may into consideration includenatural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcoholor stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol,1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol,trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁oxo-alcohol,tridecyl alcohol, isotridecyl alcohol and linear primary alcohols(Alfols) having from 8 to 22 carbon atoms. Some examples of such Alfolsare Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol(16-18). (“Alfol” is a registered trade mark of the company SasolLimited).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol,hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present singly or in the form of mixtures oftwo or more components, e.g. mixtures of alkyl and/or alkenyl groupsthat are derived from soybean fatty acids, palm kernel fatty acids ortallow oils.

(Alkylene-O) chains are preferably bivalent radicals of the formulae

Examples of a cycloaliphatic radical include cycloheptyl, cyclooctyland, preferably, cyclohexyl.

As non-ionic dispersants there come into consideration preferablysurfactants of formula

whereinR₂₅ is C₈-C₂₂alkyl;R₂₆ is hydrogen or C₁-C₄alkyl;Y₁, Y₂, Y₃ and Y₄ are each independently of the others hydrogen, methylor ethyl;n₂ is a number from 0 to 8; andn₃ is a number from 2 to 40.

Further important non-ionic dispersants correspond to formula

whereinR₂₇ is C₉-C₁₄alkyl;R₂₈ is C₁-C₄alkyl;Y₅, Y₆, Y₇ and Y₈ are each independently of the others hydrogen, methylor ethyl, one of the radicals Y₅, Y₆ and one of the radicals Y₇, Y₈always being hydrogen; andn₄ and n₅ are each independently of the other an integer from 4 to 8.

The non-ionic dispersants of formulae (9) to (11) can be used in theform of mixtures. For example, as surfactant mixtures there come intoconsideration non-end-group-terminated fatty alcohol ethoxylates offormula (9), e.g. compounds of formula (9) wherein

R₂₃ is C₈-C₂₂alkyl,

R₂₄ is hydrogen and

the alkylene-O chain is the radical —(CH₂—CH₂—O)—,

and also end-group-terminated fatty alcohol ethoxylates of formula (11).

Examples of non-ionic dispersants of formulae (9), (10) and (11) includereaction products of a C₁₀-C₁₃fatty alcohol, e.g. a C₁₃oxo-alcohol, withfrom 3 to 10 mol of ethylene oxide, propylene oxide and/or butyleneoxide and the reaction product of one mol of a C₁₃fatty alcohol with 6mol of ethylene oxide and 1 mol of butylene oxide, it being possible forthe addition products each to be end-group-terminated with C₁-C₄alkyl,preferably methyl or butyl.

Such dispersants can be used singly or in the form of mixtures of two ormore dispersants.

Instead of, or in addition to, the anionic or non-ionic dispersant, thegranules according to the invention may comprise a water-soluble organicpolymer as binder. Such polymers may be used singly or in the form ofmixtures of two or more polymers.

Water-soluble polymers that come into consideration are, for example,polyethylene glycols, copolymers of ethylene oxide with propylene oxide,gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones,vinylpyrrolidones, vinyl acetates, polyvinylimidazoles,polyvinylpyridine-N-oxides, copolymers of vinylpyrrolidone withlong-chain x-olefins, copolymers of vinylpyrrolidone withvinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates),copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides,copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides,quaternised copolymers of vinylpyrrolidones and dimethylaminoethylmethacrylates, terpolymers ofvinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone andmethacrylamidopropyl-trimethylammonium chloride, terpolymers ofcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of styrene and acrylic acid, polycarboxylic acids,polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose,polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate,copolymers of ethyl acrylate with methacrylate and methacrylic acid,copolymers of maleic acid with unsaturated hydrocarbons, and also mixedpolymerisation products of the mentioned polymers.

Of those organic polymers, special preference is given to polyethyleneglycols, carboxymethyl cellulose, polyacrylamides, polyvinyl alcohols,polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, copolymers of ethyl acrylate with methacrylate andmethacrylic acid, and polymethacrylates.

Suitable water-emulsifiable or water-dispersible binders also includeparaffin waxes.

Encapsulating materials (c) include especially water-soluble andwater-dispersible polymers and waxes. Of those materials, preference isgiven to polyethylene glycols, polyamides, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate withmethacrylate and methacrylic acid, and polymethacrylates.

Further additives (d) that come into consideration are, for example,wetting agents, dust removers, water-insoluble or water-soluble dyes orpigments, and also dissolution accelerators, optical brighteners andsequestering agents.

The preparation of the granules according to the invention is carriedout, for example, starting from:

a) a solution or suspension with a subsequent drying/shaping step or

b) a suspension of the active ingredient in a melt with subsequentshaping and solidification.

a) First of all the anionic or non-ionic dispersant and/or the polymerand, optionally, the further additives are dissolved in water andstirred, if desired with heating, until a homogeneous solution isobtained. The catalyst according to the invention is then dissolved orsuspended in the resulting aqueous solution. The solids content of thesolution should preferably be at least 30 wt-%, especially from 40 to 50wt-%, based on the total weight of the solution. The viscosity of thesolution is preferably less than 200 mPas.

The aqueous solution so prepared, comprising the catalyst according tothe invention, is then subjected to a drying step in which all water,with the exception of a residual amount, is removed, solid particles(granules) being formed at the same time. Known methods are suitable forproducing the granules from the aqueous solution. In principle, bothcontinuous methods and discontinuous methods are suitable. Continuousmethods are preferred, especially spray-drying and fluidised bedgranulation processes.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is effected e.g. using unitary or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-drying processmay be combined with an additional agglomeration of the liquid particleswith solid nuclei in a fluidised bed that forms an integral part of thechamber (so-called fluid spray). The fine particles (<100 μm) obtainedby a conventional spray-drying process may, if necessary after beingseparated from the exhaust gas flow, be fed as nuclei, without furthertreatment, directly into the atomizing cone of the atomiser of thespray-dryer for the purpose of agglomeration with the liquid droplets ofthe active ingredient.

During the granulation step, the water can rapidly be removed from thesolutions comprising the catalyst according to the invention, binder andfurther additives. It is expressly intended that agglomeration of thedroplets forming in the atomising cone, or agglomeration of dropletswith solid particles, will take place.

If necessary, the granules formed in the spray-dryer are removed in acontinuous process, for example by a sieving operation. The fines andthe oversize particles are either recycled directly to the process(without being redissolved) or are dissolved in the liquid activeingredient formulation and subsequently granulated again.

A further preparation method according to a) is a process in which thepolymer is mixed with water and then the catalyst is dissolved/suspendedin the polymer solution, thus forming an aqueous phase, the catalystaccording to the invention being homogeneously distributed in thatphase. At the same time or subsequently, the aqueous phase is dispersedin a water-immiscible liquid in the presence of a dispersion stabiliserin order that a stable dispersion is formed. The water is then removedfrom the dispersion by distillation, forming substantially dryparticles. In those particles, the catalyst is homogeneously distributedin the polymer matrix.

The granules according to the invention are resistant to abrasion, lowin dust, pourable and readily meterable. They can be added directly to aformulation, such as a detergent formulation, in the desiredconcentration of the catalyst according to the invention.

Where the coloured appearance of the granules in the detergent is to besuppressed, this can be achieved, for example, by embedding the granulesin a droplet of a whitish meltable substance (“water-soluble wax”) or byadding a white pigment (e.g. TiO₂) to the granule formulation or,preferably, by encapsulating the granules in a melt consisting, forexample, of a water-soluble wax, as described in EP-A-0 323 407, a whitesolid being added to the melt in order to reinforce the masking effectof the capsule.

b) The catalyst according to the invention can be dried in a separatestep prior to the melt-granulation and, if necessary, dry-ground in amill so that all the solids particles are <50 μm in size. The drying iscarried out in an apparatus customary for the purpose, for example in apaddle dryer, vacuum cabinet or freeze-dryer.

The finely particulate catalyst is suspended in the molten carriermaterial and homogenised. The desired granules are produced from thesuspension in a shaping step with simultaneous solidification of themelt. The choice of a suitable melt-granulation process is made inaccordance with the desired size of granules. In principle, any processwhich can be used to produce granules in a particle size of from 0.1 to4 mm is suitable. Such processes are droplet processes (withsolidification on a cooling belt or during free fall in cold air),melt-prilling (gas/liquid cooling medium), and flake formation with asubsequent comminution step, the granulation apparatus being operatedcontinuously or discontinuously.

Where the coloured appearance of the granules prepared from a melt is tobe suppressed in the detergent, in addition to the catalyst it is alsopossible to suspend in the melt white or coloured pigments which, aftersolidification, impart the desired coloured appearance to the granules(e.g. titanium dioxide).

If desired, the granules can be covered with or encapsulated in anencapsulating material. Methods that come into consideration for such anencapsulation include the customary methods and also encapsulation ofthe granules by a melt consisting e.g. of a water-soluble wax, asdescribed, for example, in EP-A-0 323 407, coacervation, complexcoacervation and surface polymerisation.

Encapsulating materials (c) include e.g. water-soluble,water-dispersible or water-emulsifiable polymers and waxes.

As further additives (d) there come into consideration, for example,wetting agents, dust removers, water-insoluble or water-soluble dyes orpigments, and also dissolution accelerators, optical brighteners andsequestering agents.

Formulations according to the invention for the cleaning of table- andkitchen-ware can be used both in household dishwashers and in industrialwashers. They are added by hand or using suitable metering devices. Theconcentrations used in the cleaning liquor are generally about from 1 to8 g/l, preferably from 2 to 5 g/l.

A machine washing programme is generally supplemented and completed by anumber of intermediate rinsing cycles with clear water after thecleaning cycle and by a clear-rinsing operation with a customary rinseagent. The use of the formulations according to the invention results,after drying, in completely clean table- and kitchen-ware that isimpeccable from the hygienic standpoint.

The following Examples serve to illustrate the invention but do notlimit the invention thereto. Parts and percentages relate to weight,unless otherwise indicated. Temperatures are in degrees Celsius, unlessotherwise indicated.

Synthesis of Compounds of the Pyrimidine Type

EXAMPLE 1 4-Chloropyridine-2-carboxylic acid ethyl ester

a) Step 1:

10.0 ml of (0.130 mol) of N,N-dimethylformamide are added dropwise at40° C., with stirring, to 295 ml (4.06 mol) of thionyl chloride. Then,in the course of half an hour, 100 g (0.812 mol) of picolinic acid areadded. The mixture is cautiously heated to 70° C. and stirred at thattemperature for 24 hours, the gases formed being conveyed away through awash bottle charged with sodium hydroxide solution. Concentration, andcoevaporation a further three times with 100 ml of toluene each time,are carried out; the product is diluted with that solvent to 440 ml, andthe solution is introduced into a mixture of 120 ml of absolute ethanoland 120 ml of toluene. The mixture is concentrated to approximately halfits volume, cooled to 4° C., filtered off under suction and washed withtoluene. 4-Chloropyridine-2-carboxylic acid ethyl ester hydrochloride isobtained in the form of a beige hygroscopic powder.

b) Step 2:

The hydrochloride obtained in Step 1 is taken up in 300 ml of ethylacetate and 200 ml of deionised water and rendered neutral with 4Nsodium hydroxide solution. After separation of the phases, extraction iscarried out twice with 200 ml of ethyl acetate each time. The organicphases are combined, dried over sodium sulfate, filtered andconcentrated. 4-Chloropyridine-2-carboxylic acid ethyl ester is obtainedin the form of a brown oil which, if required, can be purified bydistillation.

¹H-NMR (360 MHz, CDCl₃): 8.56 (d, J=5.0 Hz, 1H); 8.03 (d, J=1.8 Hz, 1H);7.39 (dd, J=5.4, 1.8 Hz, 1H); 4.39 (q, J=7.0 Hz, 2H); 1.35 (t, 3H, J=7.0Hz).

EXAMPLE 2 3-(4-Chloropyrid-2-yl)-3-oxopropionic acid ethyl ester

Under a nitrogen atmosphere, 4 g (approximately 60% dispersion inparaffin oil, about 100 mmol) of sodium hydride are washed twice with 60ml of n-hexane each time, and then 400 ml of absolute tetrahydrofuranare added. The mixture is heated to 50° C. and, in the course of 2hours, a solution of 13.36 g (72 mmol) of 4-chloropyridine-2-carboxylicacid ethyl ester and 10.04 g (114 mmol) of ethyl acetate in 60 ml ofabsolute tetrahydrofuran is added dropwise, during which the mixturebegins to boil vigorously. When the exothermic reaction has subsided,stirring is carried out for 12 hours at room temperature to complete thereaction. The yellow suspension is poured into 400 ml of ice-water andrendered neutral with 15% hydrochloric acid, and the solution isconcentrated to half its volume. Extraction is then carried out twicewith 200 ml of ethyl acetate each time, and the organic extracts arecombined, dried (sodium sulfate), filtered and concentrated. 14.5 g of3-(4-chloropyrid-2-yl)-3-oxopropionic acid ethyl ester are obtained inthe form of a light-brown oil, which is used for further syntheseswithout further purification.

¹H-NMR (360 MHz, CDCl₃): [12.33 (s, 1H, enol)]; 8.53 (d, J=5.4 Hz, 1H)[8.48 (d, J=5.4 Hz, 1H, enol)]; 8.02 (d, J=2.3 Hz, 1H) [7.88 (d, J=1.8Hz, 1H, enol)]; 7.49-7.44 (qm, 2H) [7.35-7.30 (qm, 1H, enol)]; [6.31 (s,1H, enol)]; 4.19-4.11 (m, 4H) [4.29-4.22 (qm, 2H, enol)]; 1.24-1.17 (tm,3H) [1.33-1.27 (tm, 3H, enol)].

EXAMPLE 3 6-(4-Chloropyrid-2-yl)-2-pyrid-2-yl-pyrimidin-4-ol (LigandPM1)

13.15 g (58 mmol) of 3-(4-chloropyrid-2-yl)-3-oxopropionic acid ethylester are dissolved in 400 ml of ethanol, and 9.10 g (58 mmol) of2-amidinopyridine hydrochloride are added. After the addition of 14.44ml of 4N sodium hydroxide solution, refluxing is carried out for 7hours. The mixture is cooled and concentrated to a fifth of its originalvolume. The crude product is filtered off and recrystallised frommethanol, yielding 6-(4-chloropyrid-2-yl)-2-pyrid-2-yl-pyrimidin-4-ol inthe form of beige needles.

¹H-NMR (360 MHz, CDCl₃): 12.33 (br s, 1H); 8.76 (d, J=4.5 Hz, 1H); 8.69(d, J=5.4 Hz, 1H); 8.62 (d, J=7.7 Hz, 1H); 8.50 (d, J=1.8 Hz, 1H);8.15-8.03 (tm, 1H); 7.75-7.63 (m, 2H); 7.25 (s, 1H).

EXAMPLE 46-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-ol(Ligand PM2)

A mixture of 3.51 g (12.3 mmol) of6-(4-chloropyrid-2-yl)-2-pyrid-2-yl-pyrimidin-4-ol, 27.4 ml (303 mmol,20 equivalents, 30.38 g) of 1-methyl-piperazine and 84 mg (0.05 mmol,0.05 equivalent) of zinc(II) chloride in 50 ml of 2-methyl-2-butanol isrefluxed for 22 hours and concentrated to dryness using a rotaryevaporator. 50 ml of water are added, 3.6 g of EDTA are added, and thepH is adjusted to 9 using dilute sodium hydroxide solution. Extractionis carried out three times using 150 ml of chloroform each time, and theorganic extracts are combined and dried (sodium sulfate). Concentrationis carried out using a rotary evaporator and the crude product isrecrystallised from toluene.6-[4-(4-Methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-olis obtained in the form of a whitish solid.

¹H-NMR (360 MHz, CDCl₃): 10.99 (br s, 1H); 8.56 (d, J=4.1 Hz, 1H); 8.44(d, J=7.7 Hz, 1H); 8.25 (d, J=5.9 Hz, 1H); 7.91-7.81 (tm, 1H); 7.78 (s,1H); 7.48-7.33 (tm, 1H); 6.66-6.56 (m, 1H); 3.39 (t, J=5.0 Hz, 4H); 2.53(t, J=5.0 Hz, 4H); 2.30 (s, 3H).

EXAMPLE 5 Quaternisation of6-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-olwith Methyl Iodide to Form Ligand PM3

417 mg (2.94 mmol, 0.98 equivalent) of methyl iodide are added dropwiseto a suspension of 1.045 g (3 mmol) of6-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-olin 20 ml of acetonitrile. The mixture is stirred for 14 hours at roomtemperature, then heated to 60° C. for 10 minutes and cooled, and theresulting quaternised6-[4-(4-methyl-piperazin-1-yl)pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-ol isfiltered off in the form of a white powder.

¹H-NMR (360 MHz, D₂O): 8.33 (d, J=4.5 Hz, 1H); 7.73-7.64 (m, 1H);7.64-7.56 (m, 1H); 7.42-7.31 (m, 2H); 6.78 (d, 2.3 Hz, 1H); 6.33 (s,1H); 6.31-6.26 (m, 1H).

EXAMPLE 6 2,6-Di(2-pyridyl)-4-pyrimidinol (ligand PM4)

(obtainable from Bionet, Order No. 11G-917)

EXAMPLE 7 4-Chloro-2-cyanopyridine

5.0 ml (0.16 equivalent) of N,N-dimethylformamide are added dropwise at40° C., with stirring, to 150 ml (2.06 mol) of thionyl chloride. Then,in the course of half an hour, 50 g (0.406 mol) of picolinic acid areadded. The mixture is cautiously heated to 70° C. and stirred at thattemperature for 24 hours, the gases formed being conveyed away through awash bottle charged with sodium hydroxide solution. Concentration, andcoevaporation a further three times with 50 ml of toluene each time, arecarried out. 300 ml of diethyl ether are added to the acidchloride-hydrochloride so obtained. The mixture is cooled to 0° C. usingan ice/water bath, and 250 ml of 25% ammonium hydroxide solution arecautiously added. The mixture is warmed to room temperature and stirredfor 16 hours to complete the reaction. Filtration is carried out, andthe filter residue is boiled in 400 ml of chloroform to remove secondaryproducts and recrystallised from 350 ml of methanol.4-Chloro-2-picolinic acid amide is obtained in the form of a yellowishsolid, which is reacted without further purification. 31.3 g (0.2 mol)of the amide obtained in that manner are suspended in 490 ml ofdichloromethane and cooled to 0° C. using an ice/water bath. After theaddition of 46.5 ml of N,N-dimethylformamide, 36.7 ml of phosphorusoxychloride are added dropwise in the course of 20 minutes whilemaintaining the temperature, and stirring is carried out for a further 6hours with cooling. 100 ml of water are then added and the mixture isrendered neutral with 4N sodium hydroxide solution and stirred overnightat room temperature. The organic solvent is removed using a rotaryevaporator, and the aqueous phase is extracted three times using 250 mlof chloroform each time. After concentrating and drying the crudeproduct under a high vacuum, sublimation is carried out at from 70 to90° C. and 0.2 mbar, yielding 4-chloro-2-cyanopyridine in the form of ayellowish solid.

¹H-NMR (360 MHz, CDCl₃): 8.64 (d, 5.0 Hz, 1H); 7.72 (d, J=1.8 Hz, 1H);7.56 (dd, J=5.0, 1.8 Hz, 1H).

EXAMPLE 8 2-Amidino-4-chloropyridine hydrochloride

6.93 g (50 mmol) of 4-chloro-2-cyanopyridine in 40 ml of methanol aretreated for one hour with 0.27 g (5 mmol) sodium methoxide. After theaddition of 3.00 g (56 mmol) of ammonium chloride, refluxing is carriedout for two hours. The volatile components are then removed in vacuo.The 2-amidino-4-chloropyridine hydrochloride so obtained is reactedwithout further purification.

¹H-NMR (360 MHz, D₂O): 8.61-8.57 (dm, 1H); 8.05 (s, 1H); 7.77-7.80 (m,2H).

EXAMPLE 9 2,6-Bis(4-chloropyrid-2-yl)-pyrimidin-4-ol (Ligand PM5)

The procedure is as described in the case of6-(4-chloropyrid-2-yl)-2-pyrid-2-yl-pyrimidin-4-ol (ligand PM1) inExample 3 except that, instead of 2-amidinopyridine hydrochloride, the2-amidino-4-chloropyridine hydrochloride from Example 8 is used. Afterrecrystallisation from DMSO, 2,6-bis(4-chloropyrid-2-yl)-pyrimidin-4-ol(ligand PM5) is obtained in the form of a colourless solid. ¹H-NMR (360MHz, DMSO-d₆): 12.53 (br s, 1H); 8.74 (d, J=5.0 Hz, 1H); 8.74 (s, 1H);8.71 (d, J=5.0 Hz, 1H); 8.64 (d, J=2.3 Hz, 1H); 7.83 (dd, J=5.0, 2.3 Hz,1H); 7.71 (dd, J=5.0, 2.3 Hz, 1H); 7.30 (s, 1H).

EXAMPLE 102,6-Bis[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-pyrimidin-4-ol (LigandPM6)

A mixture of 1.16 g (3.62 mmol), 8.04 ml (72 mmol) ofN-methylpiperazine, 25 mg of zinc(II) chloride and 36 ml of2-methyl-2-butanol is refluxed for 16 hours, cooled and filtered, andrecrystallisation from 2-propanol is carried out.2,6-bis[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-pyrimidin-4-ol (ligandPM6) is obtained in the form of a yellowish solid.

¹H-NMR (360 MHz, DMSO-d₆): 11.92 (br s, 1H); 8.31 (d, J=5.9 Hz, 1H);8.30 (d, J=5.9 Hz, 1H); 7.94 (br s, 2H); 7.16 (s, 1H); 7.08 (dd, J=6.3,2.7 Hz, 1H); 6.95 8 (dd, J=6.3, 2.7 Hz, 1H); 3.52-3.41 (m, 8H);2.54-2.49 (m, 4H); 2.48-2.43 (m, 4H); 2.24 (s, 6H).

EXAMPLE 11 Quaternisation of2,6-bis[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-pyrimidin-4-ol (LigandPM6) with Methyl Iodide to Form Ligand PM7

0.12 ml (1.84 mmol) of methyl iodide is added to 411 mg (0.92 mmol) of2,6-bis[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-pyrimidin-4-ol (ligandPM6) from Example 10 in 18 ml of acetonitrile. The mixture is stirredfor 16 hours at room temperature and filtered, and the residue is washedwith chloroform. The quaternised ligand PM7 is obtained in the form of acolourless solid.

¹H-NMR (360 MHz, D₂O): 8.25 (d, J=6.3 Hz, 1H); 8.19 (d, J=5.9 Hz, 1H);7.78 (d, J=2.7 Hz, 1H); 7.50 (d, J=2.3 Hz, J=1H); 7.05 (dd, J=6.3 Hz,2.7 Hz, 1H); 6.92 (dd, J=5.9 Hz, 2.3 Hz, 1H); 6.89 (s, 1H); 3.88-3.83(tm, 4H); 3.81-3.76 (tm, 4H); 3.66-3.61 (m, 8H); 2.30 (s, 3H); 2.28 (s,3H).

Synthesis of Compounds of the Triazine Type

EXAMPLE 12 4,6-di-pyrid-2-yl-[1,3,5]triazin-2-ol (Ligand TZ1)

1.0 g (approximately 60% dispersion in paraffin oil, about 25 mmol) ofsodium hydride is added in portions to a solution of 5.21 g (50 mmol) of2-cyanopyridine and 1.50 g (25 mmol) of urea in 100 ml of dimethylsulfoxide. The resulting suspension is maintained at room temperaturefor 3 hours and then heated at 75° C. for 23 hours, cooled and pouredinto 100 ml of ice-water. The mixture is rendered neutral with 2Nsulfuric acid, and the crude product is filtered off and recrystallisedfrom 55 ml of methanol, yielding 4,6-di-pyrid-2-yl-[1,3,5]triazin-2-olin the form of a white solid.

¹H-NMR (360 MHz, CD₃OD): 8.68-8.6 (m, 4H); 7.95 (ddd, J=7.7, 7.7, 1.8Hz, 2H); 7.50 (ddd, J=7.7, 4.5, 1.4 Hz, 2H).

EXAMPLE 13 4,6-Di-pyrid-2-yl-[1,3,5]triazin-2-ylamine (Ligand TZ2)

Synthesis according to F. H. Case et al., J. Am. Chem. Soc. 1959, 81,905-906.

1.0 g (approximately 60% dispersion in paraffin oil, about 25 mmol) ofsodium hydride is added in portions to a mixture of 5.21 g (50 mmol) of2-cyanopyridine and 2.39 g (25 mmol) of guanidine hydrochloride in 100ml of dimethyl sulfoxide. Stirring is carried out for 2 hours at roomtemperature, and then for 23 hours at 75° C. The mixture is cooled andpoured into 100 ml of ice-water and filtered, yielding4,6-di-pyrid-2-yl-[1,3,5]triazin-2-ylamine in the form of a white solidafter drying in vacuo.

¹H-NMR (360 MHz, DMSO-d₆): 8.82-8.73 (md, 2H); 8.44 (d, J=8.1 Hz, 2H);8.10-7.95 (tm, 2H); 7.90 (br s, 2H); 7.64-7.55 (m, 2H).

Synthesis of Metal Complexes

EXAMPLE 14 Manganese complex with6-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-ol(Ligand PM2)

503 mg (2.5 mmol) of manganese chloride tetrahydrate are added to asolution of 886 mg (2.5 mmol) of6-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-olin 200 ml of water. The solution is then freeze-dried.C₁₉H₂₀Cl₂MnN₆O×2.92H₂O, yellow solid.

Calculated C, 43.32; H, 4.94; N, 15.95; Cl, 13.46; Mn, 10.43; H₂O, 9.98.Found C, 43.10; H, 4.95; N, 16.03; Cl, 13.29; Mn, 10.4; H₂O, 9.99.

EXAMPLE 15 Manganese complex with quaternised6-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-ol(Ligand PM3)

119 mg (0.6 mmol) of manganese chloride tetrahydrate are added to asolution of 294 mg (0.6 mmol) of quaternised6-[4-(4-methyl-piperazin-1-yl)-pyrid-2-yl]-2-pyrid-2-yl-pyrimidin-4-olin 200 ml of water. The solution is then freeze-dried.C₂₀H₂₃Cl₂MnN₆O×3.75H₂O, yellowish orange solid.

Calculated C, 35.13; H, 4.50; N, 12.29; Cl, 10.37; Mn, 8.03; H₂O, 9.88.Found C, 35.38; H 5.00; N, 12.39; Cl, 10.70; Mn, 7.99; H₂O, 9.87.

APPLICATION EXAMPLES Application Example 1

Tee-stained cups were prepared according to IKW method (IKW-ArbeitskreisMaschinenspülmittel, “Methoden zur Bestimmung der Reinigungsleistung vonmaschinellen Geschirrspülmitteln (Part A and B)”, SÖFW, 11+14, 1998).Tea-stained cups were filled with a carbonate buffer solution (pH 9.6)containing 44 mM hydrogen peroxide and 20 μM catalyst. After 15 minutesthe solution was removed, the cups were rinsed with water. The removalof the tea deposit was evaluated visually on a scale from 0 (=unchanged,very strong deposit) to 10 (=no deposit). A rating of 4 was observed inreference experiments without catalyst. Results in presence of catalystsof the present invention are summarized in the following table 1: TABLE1 Mn (II) complex with ligand Rating PM 2 7 PM 3 7.5 PM 4 7 PM 6 8.5 PM7 7.1

Table 1 shows that the ratings in presence of catalysts of the presentinvention are significantly better than the reference value.

Application Example 2

Tea stained cups are prepared as in Application Example 1. The cups arecleaned in a automatic dishwasher at 50° C. using hard water (20° gH).In each cleaning programme 10 tea-stained cups were cleaned. The machinealso contained 20 clean plates and 50 g of a food mixture as describedin the IKW method as ballast. 20 g of a citrate-based formula containing6% sodium percarbonate and 2% TAED were used as dishwasher detergent.After the cleaning operation, the removal of the tea deposit isevaluated visually on a scale from 0 (=unchanged, very strong deposit)to 10 (=no deposit). A cleaning rating of 4.5 was observed withoutcatalyst. The addition of 1.8 μM of a Mn complex of ligand PM 6increased the rating to 5.0.

Application Example 3

Tea stained cups are prepared as in Application Example 1. The cups arecleaned in a automatic dishwasher at 45° C. using hard water (20° gH).In each cleaning programme 10 tea-stained cups were cleaned. The machinealso contained 20 clean plates and 50 g of a food mixture as describedin the IKW method as ballast. 20 g of a phosphate-based formulacontaining 13% sodium percarbonate were used as dishwasher detergent.Catalyst concentrations were between 75 and 100 ppm Mn (relative to thebase formulation). After the cleaning operation, the removal of the teadeposit is evaluated visually on a scale from 0 (=unchanged, very strongdeposit) to 10 (=no deposit). A rating of 5.8 was observed in referenceexperiments without catalyst. Results in presence of catalysts of thepresent invention are summarized in the following table 2: TABLE 2catalyst Mn content ppm Rating Mn complex of example 14 100 6.7 Mncomplex of ligand PM 7 100 7 Mn complex of example 14 75 6.3 Mn complexof ligand PM 6 75 6.5 Mn complex of ligand PM 4 75 7

Table 2 shows that the ratings in presence of catalysts of the presentinvention are significantly better than the reference value.

Application Example 4

Tea stained cups are prepared as in Application Example 1. The cups arecleaned in a automatic dishwasher at 50° C. using hard water (20° gH).In each cleaning programme 10 tea-stained cups were cleaned. The machinealso contained 20 clean plates and 50 g of a food mixture as describedin the IKW method as ballast. A mixture of 10 g sodium bicarbonate with1.5 g sodium carbonate was used as dishwasher detergent. 2.6 g sodiumpercarbonate and 1.2 g TAED was added as basic bleach system. Catalystconcentrations were between 1.8 and 3.6 μM. After the cleaningoperation, the removal of the tea deposit is evaluated visually on ascale from 0 (=unchanged, very strong deposit) to 10 (=no deposit). Acleaning rating of 4.8 was observed without catalyst. Results inpresence of catalysts of the present invention are summarized in thefollowing table 3: TABLE 3 Concentration catalyst complex (μM) Rating Mncomplex of example 14 3.6 5.5 Mn complex of ligand PM 6 1.8 5.4

Table 3 shows that the ratings in presence of catalysts of the presentinvention are significantly better than the reference value.

1. A method of catalyzing bleach reactions in cleaning formulations forhard surfaces comprising contacting said hard surfaces with an effectiveamount of a cleaning formulation comprising at least one metal complexof formula (1)[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1), wherein Me is manganese, titanium,iron, cobalt, nickel or copper, X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8, p is an integer having a value of from 0 to 32, z is thecharge of the metal complex, Y is a counter-ion, q=z/(charge of Y), andL is a ligand of formula (2)

wherein Q is N or CR₁₀, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ areeach independently of the others hydrogen; unsubstituted or substitutedC₁-C₁₈alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro;—COOR₁₁ or —SO₃R₁₁ wherein R₁₁ is in each case hydrogen, a cation orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein R₁₂ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;—N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or—N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein R₁₃, R₁₄ and R₁₅ are each independentlyof the other(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl, or R₁₃ and R₁₄, together with thenitrogen atom linking them, form an unsubstituted or substituted 5-, 6-or 7-membered ring which may contain further hetero atoms.
 2. A methodaccording to claim 1, wherein Me is Mn(II) and/or Fe(II).
 3. A methodaccording to claim 1 wherein L are ligands of formula (3a) and/or (3b)

wherein R′₅ is C₁-C₄alkoxy; hydroxy; N-mono- or N,N-di-C₁-C₄alkylaminounsubstituted or substituted by hydroxy in the alkyl moiety; or—NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₁₂alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₄alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen, unsubstituted or hydroxy-substituted C₁-C₁₂alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl, and R′₃ and R′₇ are each independently ofthe other hydrogen; C₁-C₄alkoxy; hydroxy; N-mono- orN,N-di-C₁-C₄alkylamino substituted by hydroxy in the alkyl moiety; or—NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₁₂alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₄alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen; unsubstituted or hydroxy-substituted C₁-C₁₂alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl.
 4. A method according to claim 1 whereinat least one Mn(II)-complex of formula (3c) and/or (3d)

wherein R′₅ is hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety; or —NR₁₃R₁₄;—(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;—N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₄alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₂alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen, unsubstituted or hydroxy-substituted C₁-C₄alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl, and R′₃ and R′₇ are each independently ofthe other hydrogen; halogen; hydroxy; N-mono- or N,N-di-C₁-C₂alkylaminosubstituted by hydroxy in the alkyl moiety; or —NR₁₃R₁₄;—(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;—N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₄alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₂alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen; unsubstituted or hydroxy-substituted C₁-C₄alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl, X is F⁻; Cl⁻; Br⁻; HOO⁻; ⁻CH₃COO⁻; HCOO⁻or HO⁻, and Y is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻;NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻ is used.
 5. A method according to claim 4wherein R′₅ is hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety; or —NH₂ R₁₃ and R₁₄ areeach independently of the other hydrogen, unsubstituted or R′₃ and R′₇are each independently of the other hydrogen; Cl; hydroxy; N-mono- orN,N-di-C₁-C₂alkylamino substituted by hydroxy in the alkyl moiety;

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and Y is CH₃COO⁻; HCOO⁻;ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻.
 6. Amethod according to claim 1 wherein at least one metal complex compoundof formula (1′)[L′_(n)Me_(m)X_(p)]^(z)Y_(q)  (1′), wherein Me is manganese, titanium,iron, cobalt, nickel or copper, X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8, p is an integer having a value of from 0 to 32, z is thecharge of the metal complex, Y is a counter-ion, q=z/(charge of Y), andL′ is a ligand of formula (2′)

wherein Q is N or CR₁₀, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ areeach independently of the others hydrogen; unsubstituted or substitutedC₁-C₁₈alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro;—COOR₁₁ or —SO₃R₁₁ wherein R₁₁ is in each case hydrogen, a cation orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein R₁₂ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;—N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or—N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein R₁₃, R₁₄ and R₁₅ are each independentlyof the other(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl, or R₁₃ and R₁₄, together with thenitrogen atom linking them, form an unsubstituted or substituted 5-, 6-or 7-membered ring which may contain further hetero atoms, with theproviso that at least one of the substituents R₁ to R₁₀ contains aquaternised nitrogen atom that is not bonded directly to one of thethree rings A, B and/or C, is used.
 7. A method according to claim 6wherein at least one Mn(II)-complex of formula (3′c) and/or (3′d)

wherein R′₅ is

R′₃ and R′₇ are independently of each other are H; Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, R′₅ and R′₇is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and Y is CH₃COO⁻; HCOO⁻;ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻.
 8. Amethod according to claim 6, wherein at least one Mn(II)-complex offormula (3′c) and/or (3′d)

wherein R′₅ is

R′₃ is H; Cl; —OH; —NH₂;

R′₇ is Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, and R′₇ is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and Y is CH₃COO⁻; HCOO⁻;ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻ is used.9. A method according to claim 6 wherein the compounds of formulae (2′),(3′c) and (3′d) one quarternised nitrogen atom is present.
 10. A methodaccording to claim 6 wherein the compounds of formulae (2′), (3′c) and(3′d) two or three quarternised nitrogen atoms are present.
 11. Amethods according to claim 6 wherein the compounds of formulae (2′),(3′c) and (3′d) none of the quaternised nitrogen atoms is bondeddirectly to one of three rings A, B and/or C.
 12. A method according toany claim 1, wherein the cleaning formulations are dishwashingformulations.
 13. A method according to claim 1, wherein the cleaningformulations are automatic dishwashing formulations.
 14. A hard surfacecleaning composition comprising at least one compound of formula (1)[L_(n)Me_(m)X_(p)]^(z)Y_(q)  (1), wherein Me is manganese, titanium,iron, cobalt, nickel or copper, X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8, p is an integer having a value of from 0 to 32, z is thecharge of the metal complex, Y is a counter-ion, q=z/(charge of Y), andL is a ligand of formula (2)

wherein Q is N or CR₁₀, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ areeach independently of the others hydrogen; unsubstituted or substitutedC₁-C₁₈alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro;—COOR₁₁ or —SO₃R₁₁ wherein R₁₁ is in each case hydrogen, a cation orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein R₁₂ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;—N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or—N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein R₁₃, R₁₄ and R₁₅ are each independentlyof the other(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl, or R₁₃ and R₁₄, together with thenitrogen atom linking them, form an unsubstituted or substituted 5-, 6-or 7-membered ring which may contain further hetero atoms.
 15. A hardsurface cleaning composition according to claim 14, wherein Me is Mn(II)and/or Fe(II).
 16. A hard surface cleaning composition according toclaim 14 wherein L are ligands of formula (3a) and/or (3b)

wherein R′₅ is C₁-C₄alkoxy; hydroxy; N-mono- or N,N-di-C₁-C₄alkylaminounsubstituted or substituted by hydroxy in the alkyl moiety; or—NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₁₂alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₄alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen, unsubstituted or hydroxy-substituted C₁-C₁₂alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl-, and R′₃ and R′₇ are each independentlyof the other hydrogen; C₁-C₄alkoxy; hydroxy; N-mono- orN,N-di-C₁-C₄alkylamino substituted by hydroxy in the alkyl moiety; or—NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₁₂alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₄alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen; unsubstituted or hydroxy-substituted C₁-C₁₂alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl.
 17. A hard surface cleaning compositionaccording to claim 14 wherein at least one Mn(II)-complex of formula(3c) and/or (3d)

wherein R′₅ is hydroxy; N-mono- or N,N-di-C₁-C₂alkylamino unsubstitutedor substituted by hydroxy in the alkyl moiety; or —NR₁₃R₁₄;—(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;—N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₄alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₂alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen, unsubstituted or hydroxy-substituted C₁-C₄alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl-, and R′₃ and R′₇ are each independentlyof the other hydrogen; halogen; hydroxy; N-mono- orN,N-di-C₁-C₂alkylamino substituted by hydroxy in the alkyl moiety; or—NR₁₃R₁₄; —(C₁-C₂alkylene)-NR₁₃R₁₄; —N(R₁₂)—(C₁-C₂alkylene)-NR₁₃R₁₄;—N[(C₁-C₂alkylene)-NR₁₃R₁₄]₂; or —N(R₁₂)—N—R₁₃R₁₄, wherein R₁₂ ishydrogen; C₁-C₄alkyl or unsubstituted phenyl or phenyl substituted by(substituted in the alkyl moiety by hydroxy) N-mono- orN,N-di-C₁-C₂alkylamino-, N-phenylamino-, N-naphthylamino-, phenyl-,phenoxy- or naphthyloxy, and R₁₃ and R₁₄ are each independently of theother hydrogen; unsubstituted or hydroxy-substituted C₁-C₄alkyl,unsubstituted phenyl or phenyl substituted as indicated above, or R₁₃and R₁₄, together with the nitrogen atom linking them, form apyrrolidine, piperidine, piperazine, morpholine or azepane ring that isunsubstituted or substituted by at least one unsubstituted C₁-C₄alkyland/or substituted C₁-C₄alkyl, X is F⁻; Cl⁻; Br⁻; HOO⁻; ⁻CH₃COO⁻; HCOO⁻or HO⁻, and Y is CH₃COO⁻; HCOO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻;NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻.
 18. A hard surface cleaning compositionaccording to claim 17 wherein R′₅ is hydroxy; N-mono- orN,N-di-C₁-C₂alkylamino unsubstituted or substituted by hydroxy in thealkyl moiety; or —NH₂ R₁₃ and R₁₄ are each independently of the otherhydrogen, unsubstituted or R′₃ and R′₇ are each independently of theother hydrogen; Cl; hydroxy; N-mono- or N,N-di-C₁-C₂alkylaminosubstituted by hydroxy in the alkyl moiety;

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and Y is CH₃COO⁻; HCOO⁻;ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻.
 19. Ahard surface cleaning composition according to claim 14 wherein at leastone metal complex compound of formula (1′)[L′_(n)Me_(m)X_(p)]^(z)Y_(q)  (1′), wherein Me is manganese, titanium,iron, cobalt, nickel or copper, X is a coordinating or bridging radical,n and m are each independently of the other an integer having a value offrom 1 to 8, p is an integer having a value of from 0 to 32, z is thecharge of the metal complex, Y is a counter-ion, q=z/(charge of Y), andL′ is a ligand of formula (2′)

wherein Q is N or CR₁₀, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ areeach independently of the others hydrogen; unsubstituted or substitutedC₁-C₁₈alkyl or unsubstituted or substituted aryl; cyano; halogen; nitro;—COOR₁₁ or —SO₃R₁₁ wherein R₁₁ is in each case hydrogen, a cation orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —SR₁₂, —SO₂R₁₂ or —OR₁₂ wherein R₁₂ is in each case hydrogen orunsubstituted or substituted C₁-C₁₈alkyl or unsubstituted or substitutedaryl; —NR₁₃R₁₄; —(C₁-C₆alkylene)-NR₁₃R₁₄; —N^(⊕)R₁₃R₁₄R₁₅;—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅; —N(R₁₂)—(C₁-C₆alkylene)-NR₁₃R₁₄;—N[(C₁-C₆alkylene)-NR₁₃R₁₄]₂; —N(R₁₂)—(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅;—N[(C₁-C₆alkylene)-N^(⊕)R₁₃R₁₄R₁₅]₂; —N(R₁₂)—N—R₁₃R₁₄ or—N(R₁₂)—N^(⊕)R₁₃R₁₄R₁₅, wherein R₁₃, R₁₄ and R₁₅ are each independentlyof the other(s) hydrogen or unsubstituted or substituted C₁-C₁₈alkyl orunsubstituted or substituted aryl, or R₁₃ and R₁₄, together with thenitrogen atom linking them, form an unsubstituted or substituted 5-, 6-or 7-membered ring which may contain further hetero atoms, with theproviso that at least one of the substituents R₁ to R₁₀ contains aquaternised nitrogen atom that is not bonded directly to one of thethree rings A, B and/or C, is used.
 20. A hard surface cleaningcomposition according to claim 19 wherein at least one Mn(II)-complex offormula (3′c) and/or (3′d)

wherein R₁₅ is

R′₃ and R′₇ are independently of each other are H; Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, R′₅ and R′₇is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and Y is CH₃COO⁻; HCOO⁻;ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻.
 21. Ahard surface cleaning composition according to claim 19, wherein atleast one Mn(II)-complex of formula (3′c) and/or (3′d)

wherein R′₅ is

R′₃ is H; Cl; —OH; —NH₂;

R′₇ is Cl; —OH; —NH₂;

with the proviso that at least one of the substituents R′₃, and R′₇ is

X is F⁻; Cl⁻; Br⁻; HOO⁻; CH₃COO⁻; HCOO⁻ or HO⁻, and Y is CH₃COO⁻; HCOO⁻;ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; HSO₃ ⁻; HSO₄ ⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻ or I⁻ is used.22. A hard surface cleaning composition according to claim 20 whereinthe compounds of formulae (2′), (3′c) and (3′d) one quarternisednitrogen atom is present.
 23. A hard surface cleaning compositionaccording to claim 20 wherein the compounds of formulae (2′), (3′c) and(3′d) two or three quaternised nitrogen atoms are present.
 24. A hardsurface cleaning composition according to claim 19 wherein the compoundsof formulae (2′), (3′c) and (3′d) none of the quaternised nitrogen atomsis bonded directly to one of three rings A, B and/or C.
 25. A hardsurface cleaning composition according to claim 14 wherein saidcomposition is a dishwashing composition.
 26. A hard surface cleaningcomposition according to claim 14 wherein said composition is anautomatic dishwasher composition.